WO2016080484A1 - 新規なフッ素化不飽和環状カーボネート及びその製造方法 - Google Patents

新規なフッ素化不飽和環状カーボネート及びその製造方法 Download PDF

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WO2016080484A1
WO2016080484A1 PCT/JP2015/082542 JP2015082542W WO2016080484A1 WO 2016080484 A1 WO2016080484 A1 WO 2016080484A1 JP 2015082542 W JP2015082542 W JP 2015082542W WO 2016080484 A1 WO2016080484 A1 WO 2016080484A1
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compound
carbonate
fluorinated
preferable
alkyl group
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PCT/JP2015/082542
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English (en)
French (fr)
Japanese (ja)
Inventor
真也 ▲高▼野
真由子 ▲高▼野
明範 谷
倫明 岡田
坂田　英郎
朋生 島田
木下　信一
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ダイキン工業株式会社
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Priority to EP15861588.0A priority Critical patent/EP3205649B1/en
Priority to US15/528,017 priority patent/US10287263B2/en
Priority to PL15861588T priority patent/PL3205649T3/pl
Priority to PL20152407T priority patent/PL3667804T3/pl
Priority to CN201580062686.XA priority patent/CN107108550B/zh
Priority to EP20188635.5A priority patent/EP3750884B1/en
Priority to PL20188635T priority patent/PL3750884T3/pl
Priority to JP2016560282A priority patent/JP6458808B2/ja
Priority to EP20152407.1A priority patent/EP3667804B1/en
Publication of WO2016080484A1 publication Critical patent/WO2016080484A1/ja
Priority to US16/285,016 priority patent/US10464916B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a novel fluorinated unsaturated cyclic carbonate and a method for producing the same.
  • Patent Document 1 describes vinylene carbonates represented by the following general formula (1).
  • R 1 and R 2 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or an alkyl which may contain a halogen atom having 1 to 12 carbon atoms. Represents a group.
  • Patent Document 2 describes the following chemical formula.
  • Patent Document 3 describes a compound represented by (Formula 4).
  • R 9 and R 10 represent hydrogen, fluorine, chlorine, an alkyl group having 1 to 3 carbon atoms, or a fluorinated alkyl group, and R 9 and R 10 may be the same or different. good
  • Patent Documents 4 to 7 also describe unsaturated cyclic carbonates.
  • the unsaturated cyclic carbonate having a fluorinated alkyl group is not known at the time of filing the application, and its usefulness is not known.
  • An object of the present invention is to provide an unsaturated cyclic carbonate having a fluorinated alkyl group, and a method for producing the same, in view of the above situation.
  • the present invention relates to a general formula (1): (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms).
  • Rf is preferably a fluorinated alkyl group having 2 to 8 carbon atoms.
  • the present invention is also an electrolytic solution containing the above compound.
  • This invention is also an electrochemical device provided with the said electrolyte solution.
  • This invention is also a lithium ion secondary battery provided with the said electrolyte solution.
  • This invention is also a module provided with the said lithium ion secondary battery.
  • the present invention relates to a general formula (2-1): (Wherein X is a halogen atom) and a fluoroalkylating agent is reacted with a compound (2-1) represented by the general formula (1): (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms).
  • the present invention relates to a general formula (3-1): (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms) and a halogenating agent is reacted with general formula (3-2): (Wherein Rf is the same as described above, X represents a halogen atom), and a compound (3-2) is reacted with a base or a metal to obtain a general compound.
  • general formula (3-1) (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms) and a halogenating agent is reacted with general formula (3-2): (Wherein Rf is the same as described above, X represents a halogen atom), and a compound (3-2) is reacted with a base or a metal to obtain a general compound.
  • Formula (1) (In the formula, Rf is the same as above).
  • the present invention relates to a general formula (4-1): (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms) and carbon dioxide is reacted with general formula (4-2): (Wherein Rf is the same as above), and a reaction of compound (4-2) with a base or a metal to give a compound represented by the general formula (1): (In the formula, Rf is the same as above).
  • the present invention relates to vinylene carbonate and a general formula (5-1): Rf-X (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms, X represents a halogen atom) and the compound (5-1) is reacted to give a general formula (5-2): (Wherein Rf is the same as described above, X represents a halogen atom), and a compound (5-2) is reacted with a base or a metal to obtain a general compound.
  • Formula (1) (In the formula, Rf is the same as above).
  • an unsaturated cyclic carbonate having a fluorinated alkyl group is provided.
  • This novel unsaturated cyclic carbonate is useful as a component constituting an electrolytic solution used in an electrochemical device such as a lithium ion secondary battery.
  • novel compounds of the present invention have the general formula (1): (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms), and is a fluorinated unsaturated cyclic carbonate.
  • Rf may be a fully fluorinated alkyl group or a partially fluorinated alkyl group, but is preferably a fully fluorinated alkyl group.
  • Rf may contain an ether bond.
  • the fluorinated alkyl group may be linear or branched.
  • Rf has 8 or less carbon atoms, and preferably 6 or less. Rf may have 2 or more carbon atoms.
  • Rf represents CF 3 —, CF 3 CF 2 —, CF 3 CF 2 CF 2 —, CF 3 CF 2 CF 2 —, CF 3 CF 2 CF 2 CF 2 —, CF 3 CF 2 CF 2 CF 2 —.
  • the novel compound can be suitably produced by the following four methods.
  • the first production method is represented by the general formula (2-1):
  • Rf is a fluorinated alkyl group having 1 to 8 carbon atoms.
  • the target fluorinated unsaturated cyclic carbonate can be obtained by performing a fluoroalkylation reaction of a known halogenated unsaturated cyclic carbonate.
  • X in the general formula (2-1) is a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom, a bromine atom or an iodine atom, and a bromine atom or an iodine atom. Is particularly preferred.
  • the first production method includes a method (1-1) using a telomer as a fluoroalkylating agent, a method (1-2) using a mercury compound as a fluoroalkylating agent, and a method using a silicon compound as a fluoroalkylating agent. (1-3).
  • a compound represented by RfI (Rf is a fluorinated alkyl group having 1 to 8 carbon atoms) or RfBr (Rf is the same as above) is used. It is preferable to use a compound, and it is more preferable to use perfluoroalkyl iodide, perfluoroalkyl bromide or the like.
  • the reaction between the compound (2-1) and the fluoroalkylating agent is preferably performed in an organic solvent.
  • organic solvent diethyl ether, diisopropyl ether, ethyl methyl ether, cyclopentyl methyl ether, methyl-t-butyl ether, tetrahydrofuran and the like are preferable, cyclopentyl methyl ether, methyl-t-butyl ether, tetrahydrofuran and the like are more preferable, cyclopentyl methyl ether, Tetrahydrofuran is particularly preferred.
  • the reaction between the compound (2-1) and the fluoroalkylating agent is preferably performed in the presence of zinc and a transition metal catalyst.
  • a transition metal catalyst palladium chloride, palladium acetate, bistriphenylphosphine palladium dichloride, bis (p-cyanophenyl) palladium dichloride, tetrakistriphenylphosphine palladium, bisacetylacetonate palladium, bisdibenzylideneacetone palladium, and the like are preferable.
  • Bistriphenylphosphine palladium dichloride and tetrakistriphenylphosphine palladium are more preferable.
  • the reaction between the compound (2-1) and the fluoroalkylating agent can be carried out under ultrasonic irradiation.
  • the reaction can be quenched by adding an aqueous solution such as an aqueous sodium chloride solution.
  • an aqueous solution such as an aqueous sodium chloride solution.
  • a liquid separated into two layers is obtained. Therefore, a solution containing the compound (1) can be obtained by collecting the organic layer by a liquid separation operation.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves or the like is added, and then the desiccant is filtered off to obtain the compound (1) as a filtrate. After obtaining the solution containing, the solution may be concentrated.
  • the purification method is not limited to a purification method by distillation or sublimation, and can be purified by a known purification method such as solvent extraction, drying, filtration, distillation, concentration, column chromatography, recrystallization, and combinations thereof, if desired. .
  • Rf 2 Hg Rf is a fluorinated alkyl group having 1 to 8 carbon atoms
  • CF 3 CF 3
  • Hg Hg, (C 2 F 5 ) 2 Hg, (C 6 F 13 ) 2 Hg, or the like.
  • the reaction of the compound (2-1) and the fluoroalkylating agent is preferably performed in an organic solvent.
  • organic solvent N-methylpyrrolidone, dimethylformamide, dimethylacetamide, acetone, methyl acetate, ethyl acetate, diethyl ether, diisopropyl ether, tetrahydrofuran, glyme, tetraglyme, sulfolane and the like are preferable.
  • N-methylpyrrolidone, dimethylformamide, Dimethylacetamide, acetone, methyl acetate, ethyl acetate, diethyl ether, glyme, tetraglyme, sulfolane and the like are more preferable, and N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and sulfolane are particularly preferable.
  • the reaction between the compound (2-1) and the fluoroalkylating agent is preferably performed in the presence of a single metal or a metal salt.
  • a metal simple substance zinc, copper and the like are preferable, and copper is more preferable.
  • the metal salt copper fluoride, copper chloride, copper bromide, copper iodide and the like are preferable, and copper bromide and copper iodide are more preferable.
  • the reaction in the presence of a single metal and a metal salt is also possible.
  • the reaction can be quenched by adding an aqueous solution such as an aqueous sodium chloride solution.
  • an aqueous solution such as an aqueous sodium chloride solution.
  • a liquid separated into two layers is obtained. Therefore, a solution containing the compound (1) can be obtained by collecting the organic layer by a liquid separation operation.
  • a liquid separation operation may be performed by adding a water-insoluble organic solvent to the reaction liquid in order to improve the liquid separation property.
  • a water-insoluble organic solvent include diethyl ether, diisopropyl ether, ethyl acetate and the like.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves or the like is added, and then the desiccant is filtered off to obtain the compound (1) as a filtrate. After obtaining the solution containing, the solution may be concentrated.
  • the purification method is not limited to a purification method by distillation or sublimation, and can be purified by a known purification method such as solvent extraction, drying, filtration, distillation, concentration, column chromatography, recrystallization, and combinations thereof, if desired. .
  • a fluoroalkylating agent a compound represented by RfTMS (Rf is a fluorinated alkyl group having 1 to 8 carbon atoms, and TMS is a trimethylsilyl group), or a compound represented by RfTES (Rf is the same as above, TES is a triethylsilyl group) is preferably used, and CF 3 TMS, C 2 F 5 TMS, C 4 F 9 TMS, C 6 F 13 TMS, CF 3 TES, C More preferably, 2 F 5 TES, C 4 F 9 TES, C 6 F 13 TES, or the like is used.
  • the reaction of the compound (2-1) and the fluoroalkylating agent is preferably performed in an organic solvent.
  • organic solvent N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylpropyleneurea, glyme, tetraglyme, sulfolane and the like are preferable, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylpropyleneurea and the like are more preferable, N -Methylpyrrolidone, dimethylformamide, dimethylpropyleneurea are particularly preferred.
  • the reaction between the compound (2-1) and the fluoroalkylating agent is preferably performed in the presence of a copper salt and a metal fluoride.
  • the copper salt is preferably copper fluoride, copper chloride, copper bromide, copper iodide, copper acetate or the like, and more preferably copper chloride or copper iodide.
  • the metal fluoride lithium fluoride, sodium fluoride, potassium fluoride and the like are preferable, and potassium fluoride is more preferable.
  • the reaction between the compound (2-1) and the fluoroalkylating agent can be performed in the presence of a ligand.
  • a ligand 1,10-phenanthroline, tetramethylethylenediamine, 2,2'-bipyridine and the like are preferable, and 1,10-phenanthroline and 2,2'-bipyridine are particularly preferable.
  • the reaction can be quenched by adding an aqueous solution such as an aqueous sodium chloride solution.
  • an aqueous solution such as an aqueous sodium chloride solution.
  • a liquid separated into two layers is obtained. Therefore, a solution containing the compound (1) can be obtained by collecting the organic layer by a liquid separation operation.
  • a liquid separation operation may be performed by adding a water-insoluble organic solvent to the reaction solution in order to improve the liquid separation property.
  • a water-insoluble organic solvent include diethyl ether, diisopropyl ether, ethyl acetate and the like.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves or the like is added, and then the desiccant is filtered off to obtain the compound (1) as a filtrate. After obtaining the solution containing, the solution may be concentrated.
  • the purification method is not limited to a purification method by distillation or sublimation, and can be purified by a known purification method such as solvent extraction, drying, filtration, distillation, concentration, column chromatography, recrystallization, and combinations thereof, if desired. .
  • the second production method is represented by the general formula (3-1):
  • a target fluorinated unsaturated cyclic carbonate can be obtained by performing a halogenation reaction of a known fluorinated saturated cyclic carbonate and then performing a dehydrohalogenation reaction.
  • the fluorinated saturated cyclic carbonate obtained by the halogenation reaction does not need to be isolated and can be directly subjected to a dehydrohalogenation reaction.
  • Rf in general formula (3-1) and general formula (3-2) is the same as Rf in general formula (1) described above.
  • X in the general formula (3-2) is a halogen atom, and among them, a chlorine atom, a bromine atom, and an iodine atom are preferable.
  • halogenating agent a halogen simple substance such as fluorine (F 2 ), chlorine (Cl 2 ), bromine (Br 2 ), iodine (I 2 ), or a halogenating reagent can be used.
  • F 2 ), chlorine (Cl 2 ), bromine (Br 2 ) or halogenating reagents are preferred.
  • the reaction of the compound (3-1) and halogen alone can be carried out in a solvent, preferably in an organic solvent such as a halogen-containing solvent.
  • the organic solvent is preferably a fluorine-containing solvent when fluorine is used as the halogen, and is preferably carried out in an organic solvent such as carbon tetrachloride when chlorine, bromine or iodine is used.
  • the above reaction can be carried out in an organic solvent.
  • the organic solvent in this case is not particularly limited as long as it is an organic solvent that does not react with the base used in the next step.
  • halogenating reagent those having a fluorine atom (fluorinating agent), those having a chlorine atom (chlorinating agent), those having a bromine atom (brominating agent), and those having an iodine atom (iodination) Agent).
  • Fluorinating agents include 1-fluoropyridinium tetrafluoroborate, 1-fluoropyridinium triflate, 1-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate, 1-fluoro-2,4,6-trifluoromethyl Pyridinium trifluoromethanesulfonate, N-fluoro-N ′-(chloromethyl) -triethylenediaminebis (tetrafluoroborate), N-fluorobenzenesulfonimide, tetrabutylammonium difluorotriphenyltin, 2,6-dichloro-1-fluoro And pyridinium trifluoromethanesulfonate, 1,1′-difluoro-2,2′-bipyridinium bis (tetrafluoroborate) and the like, and N-fluoro-N ′-(chloromethyl) -triethylenediaminebi (Tetrafluo
  • chlorinating agent examples include tert-butyl hypochlorite, N-chlorophthalimide, N-chlorosuccinimide, cyanuric chloride, oxalyl chloride, sodium dichloroisocyanurate, trichloroisocyanuric acid, trichloromethane, thionyl chloride, and the like.
  • N-chlorophthalimide, N-chlorosuccinimide, oxalyl chloride, trichloromethane, or thionyl chloride is preferred.
  • brominating agents include boron tribromide, N-bromoacetamide, bromodimethylbromide, N-bromophthalimide, N-bromosaccharin, N-bromosuccinimide, 1-butyl-3-methylimidazolium tribromide, 1, 3-dibromo-5,5-dimethylhydantoin, dibromoisocyanuric acid, 5,5-dibromomerdolic acid, 4-dimethylaminopyridinium bromide perbromide, pyridinium bromide perbromide, 2,4,4,6-tetrabromo-2, Examples include 5-cyclohexadienone, tetrabutylammonium tribromide, trimethylphenylammonium bromide, triphenylphosphine dibromide, boron tribromide, N-bromophthalimide, N-bromosuccinimide, 1,3-dibromo-5 , 5-D
  • iodinating agent examples include 1,3-diiodo-5,5-dimethylhydantoin, N-iodosaccharin, N-iodosuccinimide and the like.
  • the reaction between the compound (3-1) and the halogen alone can proceed by heating or irradiation with light.
  • light ultraviolet rays are preferable.
  • the reaction can then be quenched by adding a reducing agent.
  • the reducing agent can be added as an aqueous solution.
  • a liquid separated into two layers can be obtained by adding a reducing agent aqueous solution to the reaction product.
  • the solution containing the compound (3-2) can be obtained by recovering the organic layer.
  • the compound (3-2) is reacted with a base or a metal.
  • the above reaction can be carried out in the solvent used in the reaction for obtaining compound (3-2).
  • a solvent different from the solvent used in the reaction for obtaining the compound (3-2) is added, and the compound (3 -2) may be reacted with a base or a metal.
  • the base either an organic base or an inorganic base can be used, and triethylamine, diisopropylethylamine, and tert-butoxypotassium are particularly preferable.
  • Zinc is preferable as the metal.
  • the base or metal may be added to a solution containing the recovered compound (3-2) after adding a reducing agent to quench the reaction.
  • the reducing agent and the base or metal may be added simultaneously to the solution obtained by reacting the compound (3-1) with the halogenating agent. In this case, the two steps are carried out successively in the same vessel. can do.
  • the reaction can then be quenched by adding an acidic aqueous solution.
  • an acidic aqueous solution is added to the reaction product to obtain a liquid separated into two layers. By collecting the organic layer, a solution containing the compound (1) can be obtained.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves or the like is added, and then the desiccant is filtered off to obtain the compound (1) as a filtrate. After obtaining the solution containing, the solution may be concentrated.
  • the purification method is not limited to a purification method by distillation or sublimation, and can be purified by a known purification method such as solvent extraction, drying, filtration, distillation, concentration, column chromatography, recrystallization, and combinations thereof, if desired. .
  • the third production method is represented by the general formula (4-1): (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms) and carbon dioxide is reacted with general formula (4-2): (Wherein Rf is the same as described above), and the reaction of compound (4-2) with a base gives general formula (1): (Wherein Rf is the same as described above).
  • carbon dioxide is allowed to act on a known fluorinated epoxy compound to obtain a fluorinated saturated cyclic carbonate, and then the desired fluorinated saturated carbonate is obtained from the obtained fluorinated saturated cyclic carbonate by a dehydrohalogenation reaction.
  • a fluorinated unsaturated cyclic carbonate can be obtained.
  • the obtained fluorinated saturated cyclic carbonate does not need to be isolated and can be directly subjected to a dehydrohalogenation reaction.
  • Rf in general formula (4-1) and general formula (4-2) is the same as Rf in general formula (1) described above.
  • the reaction of compound (4-1) and carbon dioxide can be carried out in a solvent, and the solvent may be an organic solvent or water.
  • the organic solvent N-methylpyrrolidone, dimethylformamide, acetone, methyl acetate, ethyl acetate, diethyl ether, diisopropyl ether, tetrahydrofuran, glyme, tetraglyme, sulfolane and the like are preferable, among which N-methylpyrrolidone, dimethylformamide, acetone, Methyl acetate, ethyl acetate, diethyl ether, glyme, tetraglyme, sulfolane and the like are preferable, and N-methylpyrrolidone, dimethylformamide, acetone and sulfolane are more preferable.
  • the reaction between the compound (4-1) and carbon dioxide is preferably performed in the presence of a salt.
  • the salt is preferably at least one selected from the group consisting of NaF, NaCl, NaBr, NaI, LiF, LiCl, LiBr, LiI, KF, KCl, KBr and KI, and is a group consisting of LiF, LiCl, LiBr and LiI At least one selected from the above is more preferable.
  • the reaction of the compound (4-1) and carbon dioxide can be carried out at 0 to 100 ° C., preferably 15 to 80 ° C.
  • reaction when reacting using an organic solvent, reaction can be quenched by adding water etc.
  • a solution containing the compound (4-2) can be obtained by collecting the organic layer by a liquid separation operation.
  • the water-insoluble organic solvent include diethyl ether, diisopropyl ether, ethyl acetate and the like.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves, etc. is added to the solution containing compound (4-2), and then the desiccant is filtered off to obtain a compound (4-2) as a filtrate. After obtaining a solution containing, the solution may be subjected to the next step.
  • the compound (4-2) is reacted with a base or a metal.
  • the above reaction can be carried out in the solvent used in the reaction for obtaining compound (4-2). Further, after the solvent is distilled off from the solution containing the compound (4-2), a solvent different from the solvent used in the reaction for obtaining the compound (4-2) is added, and the compound (4 -2) may be reacted with a base or a metal.
  • the base either an organic base or an inorganic base can be used, and triethylamine, diisopropylethylamine, and tert-butoxypotassium are particularly preferable.
  • Zinc is preferable as the metal.
  • the above base or metal may be added to a solution containing the compound (4-2) recovered after adding water or the like to quench the reaction.
  • water or the like and a base or a metal may be added simultaneously to the solution obtained by reacting the compound (4-1) with the halogenating agent. In this case, the two steps are carried out successively in the same vessel. can do.
  • the reaction can then be quenched by adding an acidic aqueous solution.
  • an acidic aqueous solution is added to the reaction product to obtain a liquid separated into two layers. By collecting the organic layer, a solution containing the compound (1) is obtained.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves or the like is added, and then the desiccant is filtered off to obtain the compound (1) as a filtrate. After obtaining the solution containing, the solution may be concentrated.
  • the purification method is not limited to a purification method by distillation or sublimation, and can be purified by a known purification method such as solvent extraction, drying, filtration, distillation, concentration, column chromatography, recrystallization, and combinations thereof, if desired. .
  • the fourth production method comprises vinylene carbonate and general formula (5-1): Rf-X (Wherein Rf is a fluorinated alkyl group having 1 to 8 carbon atoms, X represents a halogen atom) and the compound (5-1) is reacted to give a general formula (5-2): (Wherein Rf is the same as above, X represents a halogen atom), and a step of obtaining a compound (5-2) represented by: The compound (5-2) is reacted with a base or metal to give a general formula (1): (Wherein Rf is the same as described above).
  • a fluorinated alkyl halide is allowed to act on a known vinylene carbonate to obtain a fluorinated saturated cyclic carbonate, and then the desired fluorinated saturated cyclic carbonate is subjected to dehydrohalogenation.
  • a fluorinated unsaturated cyclic carbonate can be obtained.
  • the obtained fluorinated saturated cyclic carbonate does not need to be isolated and can be directly subjected to a dehydrohalogenation reaction.
  • Rf in general formula (5-1) and general formula (5-2) is the same as Rf in general formula (1) described above.
  • X in the general formula (5-1) and the general formula (5-2) is a halogen atom, and among them, a chlorine atom, a bromine atom and an iodine atom are preferable, and an iodine atom is particularly preferable.
  • the reaction of vinylene carbonate and compound (5-1) may be carried out without a solvent or in a solvent.
  • the solvent may be an organic solvent or water.
  • the organic solvent diethyl ether, tetrahydrofuran, ethylene glycol, hexane, benzene, toluene, benzotrifluoride, dimethylformamide, dichloromethane and the like are preferable, benzene, toluene, benzotrifluoride, dimethylformamide, dichloromethane and the like are more preferable, toluene, More preferred are benzotrifluoride and dichloromethane.
  • the reaction of vinylene carbonate and compound (5-1) can be allowed to proceed by adding a radical initiator or heating without using a radical initiator.
  • radical initiator an organic radical initiator or an inorganic radical initiator can be used.
  • azo compounds As the organic radical initiator, azo compounds, organic peroxides, and organometallic compounds are preferable.
  • the azo compound 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 4 , 4′-azobis (4-cyanovaleric acid), dimethyl-1,1′-azobis (1-cyclohexanecarboxylate), 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 '-Azobis (N-cyclohexyl-2-methylpropionamide) and the like are preferable.
  • Organic peroxides include dibenzoyl peroxide, di- (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di ( t-butylperoxy) butane, t-butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t- Hexylperoxy-2-ethylhexanoate, t-butylperoxy-2
  • a metal simple substance, a metal salt, or the like can be used as the inorganic radical initiator.
  • Zinc, copper, silver or the like is preferable as the simple metal, and the reaction may be performed in the presence of a plurality of simple metals.
  • Metal salts include Na 2 S 2 O 3 , Na 2 S 2 O 4 , CuF, CuCl, CuBr, CuI, FeCl 2 , FeBr 2 , FeSO 4 , Fe (acac) 2 , AgF, AgCl, AgBr, AgI, etc.
  • the reaction may be performed in the presence of a plurality of metal salts.
  • the reaction between vinylene carbonate and compound (5-1) is preferably carried out at 0 to 200 ° C., more preferably 20 to 150 ° C. when a radical initiator is used.
  • the reaction temperature when heating without using a radical initiator is preferably 150 to 300 ° C, more preferably 200 to 250 ° C.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves, etc. is added to the solution containing compound (5-2), and then the desiccant is filtered off to obtain a compound (5-2) as a filtrate. After obtaining a solution containing, the solution may be subjected to the next step.
  • the compound (5-2) is reacted with a base or a metal.
  • the above reaction can be carried out in a solvent.
  • the solvent is not particularly limited as long as it is an organic solvent, and for example, the solvent used in the reaction for obtaining the compound (5-2) can be used. Further, after the solvent is distilled off from the solution containing the compound (5-2), a solvent different from the solvent used in the reaction for obtaining the compound (5-2) is added, and the compound (5 -2) may be reacted with a base or a metal. Further, after the reaction for obtaining the compound (5-2) is carried out in the absence of a solvent, the volatile component in the reaction solution is distilled off if necessary, then the necessary solvent is introduced and the compound is introduced in the solvent. (5-2) may be reacted with a base or a metal.
  • the base either an organic base or an inorganic base can be used, and triethylamine, diisopropylethylamine, and tert-butoxypotassium are particularly preferable.
  • Zinc is preferable as the metal.
  • the base or metal may be added to a solution containing the compound (5-2) recovered after adding water or the like to quench the reaction. Further, water or the like and a base or metal may be added simultaneously to the solution obtained by reacting vinylene carbonate and compound (5-1). In this case, the two steps are carried out continuously in the same vessel. be able to.
  • the reaction can then be quenched by adding an acidic aqueous solution.
  • an acidic aqueous solution is added to the reaction product to obtain a liquid separated into two layers. By collecting the organic layer, a solution containing the compound (1) is obtained.
  • a desiccant such as magnesium sulfate, sodium sulfate hydrate (sodium salt), molecular sieves or the like is added, and then the desiccant is filtered off to obtain the compound (1) as a filtrate. After obtaining the solution containing, the solution may be concentrated.
  • the purification method is not limited to a purification method by distillation or sublimation, and can be purified by a known purification method such as solvent extraction, drying, filtration, concentration, column chromatography, recrystallization, and combinations thereof, if desired.
  • novel compound is useful as a component constituting an electrolytic solution used in an electrochemical device such as a lithium ion secondary battery.
  • the electrolytic solution preferably contains a compound represented by the general formula (1), and more preferably contains a solvent and an electrolyte salt.
  • An electrolytic solution containing the compound represented by the general formula (1) has a high recovery capacity and a small gas generation amount even when stored at a high temperature.
  • the electrolytic solution preferably contains 0.001 to 90% by volume of the compound represented by the general formula (1) with respect to the solvent.
  • the content of the compound represented by the general formula (1) is more preferably 0.01% by volume or more, more preferably 60% by volume or less, and further preferably 20% by volume or less. It is particularly preferable that the volume is not more than%.
  • the solvent preferably further contains at least one selected from the group consisting of a fluorinated chain carbonate, a non-fluorinated saturated cyclic carbonate, a fluorinated saturated cyclic carbonate, and a non-fluorinated chain carbonate.
  • the fluorinated chain carbonate is a chain carbonate having a fluorine atom.
  • the fluorinated chain carbonate preferably has a fluorine content of 10 to 70% by mass.
  • the fluorine content is a value calculated from ⁇ (number of fluorine atoms ⁇ 19) / molecular weight of fluorinated chain carbonate ⁇ ⁇ 100 (%) based on the structural formula of the fluorinated chain carbonate.
  • the fluorinated chain carbonate has a general formula: Rf 1 OCOORf 2 (Wherein Rf 1 and Rf 2 are the same or different and represent an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group, provided that at least one of Rf 1 and Rf 2 contains 1 to 4 carbon atoms.
  • a fluorinated chain carbonate represented by fluorinated alkyl group
  • Rf 1 and Rf 2 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group. However, at least one of Rf 1 and Rf 2 is a fluorine-containing alkyl group having 1 to 4 carbon atoms. The number of carbon atoms is preferably 1 to 3 in view of good compatibility with the electrolytic solution.
  • Rf 1 examples include CF 3 —, CF 3 CF 2 —, (CF 3 ) 2 CH—, CF 3 CH 2 —, C 2 F 5 CH 2 —, HCF 2 CH 2 —, HCF 2 CF 2 CH 2- , CF 3 CFHCF 2 CH 2- and the like.
  • CF 3 CH 2 — and HCF 2 CH 2 — are preferred because they have high flame retardancy and good rate characteristics and oxidation resistance.
  • Rf 2 examples include CF 3- , CF 3 CF 2- , (CF 3 ) 2 CH-, CF 3 CH 2- , C 2 F 5 CH 2- , HCF 2 CH 2- , HCF 2 CF 2 CH 2- , CF 3 CFHCF 2 CH 2- and the like.
  • CF 3 CH 2 — and HCF 2 CH 2 — are preferred because they have high flame retardancy and good rate characteristics and oxidation resistance.
  • fluorinated chain carbonate examples include, for example, CF 3 CH 2 OCOOCH 2 CF 3 , CF 3 CH 2 OCOOCH 3 , CF 3 CF 2 CH 2 OCOOCH 2 CF 2 CF 3 , and CF 3 CF 2 CH 2 OCOOCH.
  • Fluorinated chain carbonates such as 3 .
  • compounds described in JP-A-06-21992, JP-A-2000-327634, JP-A-2001-256983 and the like can also be exemplified.
  • CF 3 CH 2 OCOOCH 2 CF 3 , CF 3 CH 2 OCOOCH 3 , and CF 3 CF 2 CH 2 OCOOCH 2 CF are highly effective in suppressing gas generation and improving high-temperature storage characteristics.
  • the fluorine content is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 33% by mass or more.
  • the fluorine content is preferably 60% by mass or less, and more preferably 55% by mass or less.
  • non-fluorinated saturated cyclic carbonate examples include ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate.
  • the non-fluorinated saturated cyclic carbonate is at least one compound selected from the group consisting of ethylene carbonate, propylene carbonate, and butylene carbonate in that the dielectric constant is high and the viscosity is suitable. It is preferable.
  • 1 type of the compound mentioned above may be used, and 2 or more types may be used together.
  • the fluorinated saturated cyclic carbonate is a saturated cyclic carbonate to which a fluorine atom is added.
  • X 1 to X 4 are the same or different and are each —H, —CH 3 , —F, a fluorinated alkyl group optionally having an ether bond, or fluorine optionally having an ether bond
  • at least one of X 1 to X 4 is —F, a fluorinated alkyl group that may have an ether bond, or a fluorinated alkoxy group that may have an ether bond
  • Fluorinated saturated cyclic carbonate (A) represented by: When the fluorinated saturated cyclic carbonate (A) is contained, when the electrolytic solution is applied to a lithium ion secondary battery or the like, a stable film can be formed on the negative electrode, and a side reaction of the electrolytic solution at the negative electrode can be caused. It can be sufficiently suppressed. As a result, extremely stable and excellent charge / discharge characteristics can be obtained.
  • the “ether bond” is a bond represented by —O—.
  • one or two of X 1 to X 4 are —F, a fluorinated alkyl group optionally having an ether bond, or A fluorinated alkoxy group which may have an ether bond is preferable.
  • X 1 to X 4 are —H, —F, fluorinated alkyl, since it is expected to lower the viscosity at low temperature, increase the flash point, and further improve the solubility of the electrolyte salt.
  • the group (a), a fluorinated alkyl group (b) having an ether bond, or a fluorinated alkoxy group (c) is preferred.
  • the fluorinated alkyl group (a) is obtained by substituting at least one hydrogen atom of the alkyl group with a fluorine atom.
  • the number of carbon atoms in the fluorinated alkyl group (a) is preferably 1-20, more preferably 2-17, still more preferably 2-7, and particularly preferably 2-5. If the carbon number is too large, the low-temperature characteristics may be lowered or the solubility of the electrolyte salt may be lowered. If the carbon number is too small, the solubility of the electrolyte salt is lowered, the discharge efficiency is lowered, and further, An increase in viscosity may be observed.
  • fluorinated alkyl groups (a) those having 1 carbon atom include CFH 2 —, CF 2 H—, and CF 3 —.
  • fluorinated alkyl groups (a) those having 2 or more carbon atoms are represented by the following general formula (a-1): R 1 -R 2- (a-1)
  • R 1 is an alkyl group having 1 or more carbon atoms which may have a fluorine atom
  • R 2 is an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom; provided that R 1 and A fluorinated alkyl group represented by (at least one of R 2 has a fluorine atom) can be preferably exemplified from the viewpoint of good solubility of the electrolyte salt.
  • R 1 and R 2 may further have other atoms other than the carbon atom, the hydrogen atom, and the fluorine atom.
  • R 1 is an alkyl group having 1 or more carbon atoms which may have a fluorine atom.
  • R 1 is preferably a linear or branched alkyl group having 1 to 16 carbon atoms.
  • the number of carbon atoms of R 1 is more preferably 1 to 6, and further preferably 1 to 3.
  • R 1 specifically, as a linear or branched alkyl group, CH 3 —, CH 3 CH 2 —, CH 3 CH 2 CH 2 —, CH 3 CH 2 CH 2 CH 2 —,
  • R 1 is a linear alkyl group having a fluorine atom, CF 3 —, CF 3 CH 2 —, CF 3 CF 2 —, CF 3 CH 2 CH 2 —, CF 3 CF 2 CH 2 — CF 3 CF 2 CF 2- , CF 3 CH 2 CF 2- , CF 3 CH 2 CH 2 CH 2- , CF 3 CF 2 CH 2 CH 2- , CF 3 CH 2 CF 2 CH 2- , CF 3 CH 2 CF 2 CH 2- , CF 3 CF 2 CF 2 CH 2 —, CF 3 CF 2 CF 2 CH 2 —, CF 3 CF 2 CH 2 CF 2 —, CF 3 CH 2 CH 2 CF 2 —, CF 3 CH 2 CH 2 CH 2 —, CF 3 CF 2 CH 2 CH 2 —, CF 3 CF 2 CH 2 CH 2 CH 2 —, CF 3 CF 2 CH 2 CH 2 —, CF 3 CF 2 CF 2 CH 2 CH 2 —,
  • R 1 is a branched alkyl group having a fluorine atom
  • the broken line in the formula is a binding site.
  • the like are preferable. However, since the viscosity tends to be high if there is a branch of —CH 3 or —CF 3 , the number is preferably small (one) or zero.
  • R 2 is an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom.
  • R 2 may be linear or branched.
  • An example of the minimum structural unit constituting such a linear or branched alkylene group is shown below.
  • R 2 is composed of these alone or in combination.
  • the base is composed of a constitutional unit that does not contain Cl, because de-HCl reaction with a base does not occur and is more stable.
  • R 2 is linear, it is composed of only the above-mentioned linear minimum structural unit, and —CH 2 —, —CH 2 CH 2 — or —CF 2 — is particularly preferable. From the viewpoint of further improving the solubility of the electrolyte salt, —CH 2 — or —CH 2 CH 2 — is more preferable.
  • R 2 When R 2 is branched, it contains at least one of the above-mentioned branched minimum structural units, and R 2 is represented by the general formula: — (CX a X b ) — (X a is H, F, CH 3 or CF 3 ; X b is CH 3 or CF 3, provided that when X b is CF 3 , X a is H or CH 3 .
  • the solubility of the electrolyte salt can be further improved.
  • Preferred fluorinated alkyl groups (a) include, for example, CF 3 CF 2 —, HCF 2 CF 2 —, H 2 CFCF 2 —, CH 3 CF 2 —, CF 3 CF 2 CF 2 —, HCF 2 CF 2 CF 2 -, H 2 CFCF 2 CF 2- , CH 3 CF 2 CF 2- ,
  • the fluorinated alkyl group (b) having an ether bond is obtained by substituting at least one hydrogen atom of the alkyl group having an ether bond with a fluorine atom.
  • the fluorinated alkyl group (b) having an ether bond preferably has 2 to 17 carbon atoms. If the number of carbons is too large, the viscosity of the fluorinated saturated cyclic carbonate (A) increases, and the fluorine-containing group increases, so that the solubility of the electrolyte salt decreases due to a decrease in the dielectric constant, A decrease in compatibility may be observed. From this viewpoint, the fluorinated alkyl group (b) having an ether bond preferably has 2 to 10 carbon atoms, and more preferably 2 to 7 carbon atoms.
  • the alkylene group constituting the ether portion of the fluorinated alkyl group (b) having an ether bond may be a linear or branched alkylene group.
  • An example of the minimum structural unit constituting such a linear or branched alkylene group is shown below.
  • the alkylene group may be composed of these minimum structural units alone, and may be linear (i), branched (ii), or linear (i) and branched (ii). You may comprise by the combination. Preferred specific examples will be described later.
  • the base is composed of a constitutional unit that does not contain Cl, because de-HCl reaction with a base does not occur and is more stable.
  • fluorinated alkyl group (b) having an ether bond include a compound represented by the general formula (b-1): R 3- (OR 4 ) n1- (b-1) (Wherein R 3 may have a fluorine atom, preferably an alkyl group having 1 to 6 carbon atoms; R 4 may have a fluorine atom, preferably an alkylene having 1 to 4 carbon atoms) N1 is an integer of 1 to 3; provided that at least one of R 3 and R 4 has a fluorine atom).
  • R 3 and R 4 include the following, and these can be combined as appropriate to form a fluorinated alkyl group (b) having an ether bond represented by the general formula (b-1). However, it is not limited to these.
  • R 3 the general formula: X c 3 C— (R 5 ) n2 — (the three X c are the same or different and each is H or F; R 5 represents a fluorine atom having 1 to 5 carbon atoms)
  • R 3 includes CH 3 —, CF 3 —, HCF 2 —, and H 2 CF—.
  • R 3 is linear, CF 3 CH 2 —, CF 3 CF 2 —, CF 3 CH 2 CH 2 —, CF 3 CF 2 CH 2 —, CF 3 CF 2 CF 2 —, CF 3 CH 2 CF 2 —, CF 3 CH 2 CH 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 —, CF 3 CF 2 CF 2 CH 2- , CF 3 CF 2 CH 2 CF 2- , CF 3 CH 2 CH 2 CH 2- , CF 3 CH 2 CF 2 CH 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 CH 2 —, CF 3 CH 2 CF 2 CH 2 CH 2
  • n2 is 1, and as R 3 is branched, the
  • R 3 is more preferably linear.
  • n1 is an integer of 1 to 3, preferably 1 or 2.
  • R 4 may be the same or different.
  • R 4 include the following linear or branched ones.
  • the fluorinated alkoxy group (c) is obtained by substituting at least one hydrogen atom of the alkoxy group with a fluorine atom.
  • the fluorinated alkoxy group (c) preferably has 1 to 17 carbon atoms. More preferably, it has 1 to 6 carbon atoms.
  • the fluorinated alkoxy group (c) is represented by the general formula: X d 3 C— (R 6 ) n3 —O— (the three X d are the same or different, and all are H or F; R 6 is preferably carbon number)
  • fluorinated alkoxy group (c) examples include a fluorinated alkoxy group in which an oxygen atom is bonded to the terminal of the alkyl group exemplified as R 1 in the general formula (a-1).
  • the fluorine content of the fluorinated alkyl group (a), the fluorinated alkyl group (b) having an ether bond, and the fluorinated alkoxy group (c) in the fluorinated saturated cyclic carbonate (A) is preferably 10% by mass or more. If the fluorine content is too low, the effect of increasing the flash point may not be sufficiently obtained. From this viewpoint, the fluorine content is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is usually 85% by mass.
  • the fluorine content of the fluorinated alkyl group (a), the fluorinated alkyl group (b) having an ether bond, and the fluorinated alkoxy group (c) is determined based on ⁇ (number of fluorine atoms) based on the structural formula of each group. ⁇ 19) / Formula amount of each group ⁇ ⁇ 100 (%).
  • the fluorine content of the entire fluorinated saturated cyclic carbonate (A) is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the upper limit is usually 76% by mass.
  • the fluorine content of the fluorinated saturated cyclic carbonate (A) is determined based on the structural formula of the fluorinated saturated cyclic carbonate (A) ⁇ (number of fluorine atoms ⁇ 19) / of the fluorinated saturated cyclic carbonate (A). Molecular weight ⁇ ⁇ 100 (%).
  • fluorinated saturated cyclic carbonate (A) examples include the following.
  • Etc. can also be used.
  • fluorinated saturated cyclic carbonate (A) in which at least one of X 1 to X 4 in the general formula (A) is a fluorinated alkyl group (a) and the rest are all —H are as follows:
  • At least one of X 1 to X 4 is a fluorinated alkyl group (b) or a fluorinated alkoxy group (c) having an ether bond, and the rest are all —H.
  • fluorinated saturated cyclic carbonate (A) As a specific example of the fluorinated saturated cyclic carbonate (A),
  • the fluorinated saturated cyclic carbonate (A) is not limited to the specific examples described above. Moreover, the said fluorinated saturated cyclic carbonate (A) may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Moreover, although suitable content of a fluorinated saturated cyclic carbonate is mentioned later, these suitable contents are also suitable content of a fluorinated saturated cyclic carbonate (A).
  • fluorinated saturated cyclic carbonate (A) fluoroethylene carbonate and difluoroethylene carbonate are preferable.
  • non-fluorinated chain carbonate examples include CH 3 OCOOCH 3 (dimethyl carbonate: DMC), CH 3 CH 2 OCOOCH 2 CH 3 (diethyl carbonate: DEC), CH 3 CH 2 OCOOCH 3 (ethyl methyl carbonate: EMC). ), CH 3 OCOOCH 2 CH 2 CH 3 (methylpropyl carbonate), methyl butyl carbonate, ethyl propyl carbonate, ethyl butyl carbonate, and other hydrocarbon-based chain carbonates.
  • At least one compound selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl butyl carbonate, ethyl propyl carbonate, and ethyl butyl carbonate is preferable.
  • the solvent preferably contains 10 to 99.99% by volume of non-fluorinated saturated cyclic carbonate, fluorinated saturated cyclic carbonate, non-fluorinated chain carbonate and fluorinated chain carbonate in total. More preferably, it is 40 volume% or more, More preferably, it is 50 volume% or more, Most preferably, it is 70 volume% or more. Further, it is more preferably 99.9% by volume or less, further preferably 99.5% by volume or less, still more preferably 99% by volume or less, particularly preferably 96% by volume or less, and most preferably 80% by volume or less.
  • the solvent is selected from the group consisting of at least one saturated cyclic carbonate selected from the group consisting of non-fluorinated saturated cyclic carbonates and fluorinated saturated cyclic carbonates, and non-fluorinated chain carbonates and fluorinated chain carbonates. And at least one chain carbonate.
  • the volume ratio of the saturated cyclic carbonate to the chain carbonate is preferably 10/90 to 90/10, more preferably 30/70 or more, and more preferably 70/30 or less.
  • the electrolytic solution contains an electrolyte salt.
  • the electrolyte salt any salt that can be used for an electrolytic solution for an electrochemical device such as a secondary battery or an electric double layer capacitor can be used, and among them, a lithium salt is preferable.
  • lithium salt examples include inorganic lithium salts such as LiClO 4 , LiPF 6, and LiBF 4 ; LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3) (SO 2 C 4 F 9), LiC (SO 2 CF 3) 3, LiPF 4 (CF 3) 2, LiPF 4 (C 2 F 5) 2, LiPF 4 (SO 2 CF 3) 2, LiPF 4 (SO 2 C 2 F 5 ) 2 , LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (SO 2 CF 3 ) 2 , LiBF 2 (SO 2 C 2 F 5 ) 2, lithium difluoro (oxalato) borate, lithium bis (oxalato) borate, and the formula: LiPF a (C n F 2n + 1) 6-a ( wherein, a is It is an integer of ⁇ 5, n can be mentioned fluor
  • the lithium salt in that it is possible to suppress the deterioration after the electrolytic solution was stored at high temperatures, LiPF 6, LiBF 4, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5 ) 2 , lithium difluoro (oxalate) borate, lithium bis (oxalate) borate, and the formula: LiPF a (C n F 2n + 1 ) 6-a where a is an integer from 0 to 5, n is preferably an integer of 1 to 6, and is preferably at least one selected from the group consisting of salts represented by:
  • LiPF a (C n F 2n + 1 ) 6-a examples include LiPF 3 (CF 3 ) 3 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (C 3 F 7 ) 3 LiPF 3 (C 4 F 9 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 4 (C 2 F 5 ) 2 , LiPF 4 (C 3 F 7 ) 2 , LiPF 4 (C 4 F 9 ) 2
  • the alkyl group represented by C 3 F 7 or C 4 F 9 in the formula may be either a straight chain or a branched structure.
  • the concentration of the electrolyte salt in the electrolytic solution is preferably 0.5 to 3 mol / liter. Outside this range, the electrical conductivity of the electrolytic solution tends to be low, and the battery performance tends to deteriorate.
  • the concentration of the electrolyte salt is more preferably 0.9 mol / liter or more, and more preferably 1.5 mol / liter or less.
  • an ammonium salt is preferable.
  • the ammonium salt include the following (IIa) to (IIe).
  • R 1a , R 2a , R 3a and R 4a are the same or different, and all are alkyl groups optionally containing an ether bond having 1 to 6 carbon atoms; X ⁇ is an anion)
  • Preferred examples include quaternary ammonium salts.
  • the ammonium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance.
  • Preferred specific examples of the tetraalkyl quaternary ammonium salt include compounds represented by the general formula (IIa-1):
  • R 5a is an alkyl group having 1 to 6 carbon atoms
  • R 6a is a divalent hydrocarbon group having 1 to 6 carbon atoms
  • R 7a is an alkyl group having 1 to 4 carbon atoms
  • z is 1 or 2
  • X - is an alkyl ether group containing trialkylammonium salt represented by the anion
  • Etc By introducing an alkyl ether group, the viscosity can be lowered.
  • the anion X ⁇ may be an inorganic anion or an organic anion.
  • inorganic anions include AlCl 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , TaF 6 ⁇ , I ⁇ and SbF 6 ⁇ .
  • organic anion include CF 3 COO ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ and the like.
  • BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ and SbF 6 ⁇ are preferred from the viewpoint of good oxidation resistance and ion dissociation properties.
  • tetraalkyl quaternary ammonium salt examples include Et 4 NBF 4 , Et 4 NClO 4 , Et 4 NPF 6 , Et 4 NAsF 6 , Et 4 NSbF 6 , Et 4 NCF 3 SO 3 , Et 4 N CF 3 SO 2) 2 N, Et 4 NC 4 F 9 SO 3, Et 3 MeNBF 4, Et 3 MeNClO 4, Et 3 MeNPF 6, Et 3 MeNAsF 6, Et 3 MeNSbF 6, Et 3 MeNCF 3 SO 3, Et 3 MeN (CF 3 SO 2 ) 2 N, Et 3 MeNC 4 F 9 SO 3 , N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium salt and the like, and particularly, Et 4 NBF. 4, Et 4 NPF 6, Et 4 NSbF 6, Et 4 NAsF 6, Et 3 MeNBF 4, N, - Diethyl -N- methyl -N- (2-methoxyethyl) ammonium salts are preferred.
  • R 8a and R 9a are the same or different and each is an alkyl group having 1 to 4 carbon atoms; X - is an anion; n2 is an integer of 0 to 5; n1 is an integer of 0 to 5) represented by Spirocyclic bipyrrolidinium salt, general formula (IIb-2):
  • R 10a and R 11a are the same or different and each is an alkyl group having 1 to 4 carbon atoms;
  • X - is an anion;
  • n4 is an integer of 0 to 5;
  • n3 is an integer of 0 to 5
  • R 12a and R 13a are the same or different and each is an alkyl group having 1 to 4 carbon atoms; X - is an anion; n6 is an integer of 0 to 5; n5 is an integer of 0 to 5) represented by Spiro ring bipyrrolidinium salts are preferred.
  • the spiro-ring bipyrrolidinium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance.
  • Anion X - of the preferred embodiment are the same as for (IIa). Among them, high dissociative, terms the internal resistance is low under a high voltage, BF 4 -, PF 6 - , (CF 3 SO 2) 2 N- or (C 2 F 5 SO 2) 2 N- is preferable.
  • spiro ring bipyrrolidinium salt examples include, for example,
  • This spiro ring bipyrrolidinium salt is excellent in terms of solubility in a solvent, oxidation resistance, and ionic conductivity.
  • R 14a and R 15a are the same or different, and both are alkyl groups having 1 to 6 carbon atoms; X 2 ⁇ is an anion)
  • the imidazolium salt shown by can be illustrated preferably.
  • the imidazolium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance.
  • imidazolium salts include, for example,
  • This imidazolium salt is excellent in terms of low viscosity and good solubility.
  • N-alkylpyridinium salts represented by the formula are preferred.
  • the N-alkylpyridinium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance.
  • N-alkylpyridinium salts include, for example,
  • This N-alkylpyridinium salt is excellent in that it has low viscosity and good solubility.
  • N, N-dialkylpyrrolidinium salt represented by the formula is preferably exemplified. Further, the oxidation resistance of the N, N-dialkylpyrrolidinium salt in which part or all of the hydrogen atoms are substituted with fluorine atoms and / or fluorine-containing alkyl groups having 1 to 4 carbon atoms is improved. It is preferable from the point.
  • N, N-dialkylpyrrolidinium salts include, for example,
  • This N, N-dialkylpyrrolidinium salt is excellent in that it has low viscosity and good solubility.
  • ammonium salts (IIa), (IIb) and (IIc) are preferable in terms of good solubility, oxidation resistance and ionic conductivity,
  • a lithium salt for example, LiAsF 6 , LiSbF 6 , and LiN (SO 2 C 2 H 5 ) 2 are preferable.
  • a magnesium salt may be used.
  • Mg (ClO 4 ) 2 , Mg (OOC 2 H 5 ) 2 and the like are preferable.
  • the concentration is preferably 0.6 mol / liter or more. If it is less than 0.6 mol / liter, not only the low-temperature characteristics are deteriorated, but also the initial internal resistance is increased.
  • the concentration of the electrolyte salt is more preferably 0.9 mol / liter or more.
  • the upper limit of the concentration is preferably 3.0 mol / liter or less, and more preferably 2.0 mol / liter or less in terms of low temperature characteristics.
  • the ammonium salt is triethylmethylammonium tetrafluoroborate (TEMABF 4 )
  • the concentration is preferably 0.8 to 1.9 mol / liter from the viewpoint of excellent low-temperature characteristics.
  • SBPBF 4 spirobipyrrolidinium tetrafluoroborate
  • it is preferably 0.7 to 2.0 mol / liter.
  • the electrolyte solution preferably further contains polyethylene oxide having a weight average molecular weight of 2000 to 4000 and having —OH, —OCOOH, or —COOH at the terminal.
  • polyethylene oxide having a weight average molecular weight of 2000 to 4000 and having —OH, —OCOOH, or —COOH at the terminal.
  • the stability of the electrode interface can be improved and the battery characteristics can be improved.
  • the polyethylene oxide include polyethylene oxide monool, polyethylene oxide carboxylic acid, polyethylene oxide diol, polyethylene oxide dicarboxylic acid, polyethylene oxide triol, and polyethylene oxide tricarboxylic acid. These may be used alone or in combination of two or more. Of these, a mixture of polyethylene oxide monool and polyethylene oxide diol and a mixture of polyethylene oxide carboxylic acid and polyethylene oxide dicarboxylic acid are preferable in terms of better battery characteristics.
  • the weight average molecular weight of the polyethylene oxide is too small, it may be easily oxidized and decomposed.
  • the weight average molecular weight is more preferably 3000 to 4000.
  • the said weight average molecular weight can be measured by polystyrene conversion by a gel permeation chromatography (GPC) method.
  • the polyethylene oxide content is preferably 1 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 2 mol / kg in the electrolytic solution. When there is too much content of the said polyethylene oxide, there exists a possibility that a battery characteristic may be impaired.
  • the polyethylene oxide content is more preferably 5 ⁇ 10 ⁇ 6 mol / kg or more.
  • the electrolyte solution is further selected from the group consisting of unsaturated cyclic carbonates (excluding the compound represented by the general formula (1)), fluorinated saturated cyclic carbonates, and cyclic sulfonic acid compounds as additives. It is preferable to contain at least one kind. By containing these compounds, deterioration of battery characteristics can be suppressed.
  • the unsaturated cyclic carbonate is a cyclic carbonate containing an unsaturated bond, that is, a cyclic carbonate having at least one carbon-carbon unsaturated bond in the molecule.
  • vinylene carbonate compounds such as vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate; 4-vinyl ethylene carbonate (VEC), 4- Methyl-4-vinylethylene carbonate, 4-ethyl-4-vinylethylene carbonate, 4-n-propyl-4-vinylethylene carbonate, 5-methyl-4-vinylethylene carbonate, 4,4-divinylethylene carbonate, 4, And vinyl ethylene carbonate compounds such as 5-divinylethylene carbonate, 4,4-dimethyl-5-methylene ethylene carbonate, and 4,4-diethyl-5-methylene ethylene carbonate.
  • the molecular weight of the unsaturated cyclic carbonate is not particularly limited, and is arbitrary as long as the performance as an electrolytic solution is not significantly impaired.
  • the molecular weight is preferably 50 or more and 250 or less. If it is this range, it will be easy to ensure the solubility of the unsaturated cyclic carbonate with respect to electrolyte solution, and the performance of electrolyte solution will fully be expressed easily.
  • the molecular weight of the unsaturated cyclic carbonate is more preferably 80 or more, and more preferably 150 or less.
  • a fluorinated unsaturated cyclic carbonate can also be used suitably.
  • the number of fluorine atoms contained in the fluorinated unsaturated cyclic carbonate is not particularly limited as long as it is 1 or more. Among them, the number of fluorine atoms is usually 6 or less, preferably 4 or less, and most preferably 1 or 2 fluorine atoms.
  • fluorinated unsaturated cyclic carbonate examples include a fluorinated vinylene carbonate derivative, a fluorinated ethylene carbonate derivative substituted with an aromatic ring or a substituent having a carbon-carbon double bond.
  • Fluorinated vinylene carbonate derivatives include 4-fluoro vinylene carbonate, 4-fluoro-5-methyl vinylene carbonate, 4-fluoro-5-phenyl vinylene carbonate, 4-allyl-5-fluoro vinylene carbonate, 4-fluoro-5- And vinyl vinylene carbonate.
  • fluorinated ethylene carbonate derivative substituted with a substituent having an aromatic ring or a carbon-carbon double bond examples include 4-fluoro-4-vinylethylene carbonate, 4-fluoro-4-allylethylene carbonate, 4-fluoro-5 -Vinylethylene carbonate, 4-fluoro-5-allylethylene carbonate, 4,4-difluoro-4-vinylethylene carbonate, 4,4-difluoro-4-allylethylene carbonate, 4,5-difluoro-4-vinylethylene carbonate 4,5-difluoro-4-allylethylene carbonate, 4-fluoro-4,5-divinylethylene carbonate, 4-fluoro-4,5-diallylethylene carbonate, 4,5-difluoro-4,5-divinylethylene carbonate , 4,5-diflu B-4,5-diallylethylene carbonate, 4-fluoro-4-phenylethylene carbonate, 4-fluoro-5-phenylethylene carbonate, 4,4-difluoro-5-phenyl
  • the molecular weight of the fluorinated unsaturated cyclic carbonate is not particularly limited, and is arbitrary as long as the performance as an electrolytic solution is not significantly impaired.
  • the molecular weight is preferably 50 or more and 500 or less. If it is this range, it will be easy to ensure the solubility of the fluorinated unsaturated cyclic carbonate with respect to electrolyte solution, and the performance of electrolyte solution will be easy to be expressed.
  • the said unsaturated cyclic carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • fluorinated saturated cyclic carbonate As said fluorinated saturated cyclic carbonate, the compound illustrated as a fluorinated saturated cyclic carbonate which can be used for the said solvent can be mentioned.
  • the cyclic sulfonic acid compound examples include 1,3-propane sultone, 1,4-butane sultone, 1-fluoro-1,3-propane sultone, 2-fluoro-1,3-propane sultone, and 3-fluoro-1 , 3-propane sultone and the like.
  • the electrolyte solution preferably contains 1,3-propane sultone and / or 1,4-butane sultone in that the high temperature characteristics can be improved.
  • the content thereof is 0.1 to 10 in the electrolytic solution. It is preferable that it is mass%, 1 mass% or more is more preferable, and 5 mass% or less is more preferable.
  • the above electrolyte solution is a cyclic and chain carboxylic acid ester, an ether compound, a nitrogen-containing compound, a boron-containing compound, an organic silicon-containing compound, a non-flammable (flame retardant) agent, and a surface activity as long as the performance as an electrolyte solution is not impaired. It may further contain other solvents or additives such as agents, high dielectric additives, cycle and rate characteristics improvers, or overcharge inhibitors.
  • Examples of the cyclic carboxylic acid ester include those having 3 to 12 total carbon atoms in the structural formula. Specific examples include gamma butyrolactone, gamma valerolactone, gamma caprolactone, epsilon caprolactone, and the like. Among these, gamma butyrolactone is particularly preferable from the viewpoint of improving battery characteristics resulting from an improvement in the degree of lithium ion dissociation.
  • the compounding quantity of cyclic carboxylic acid ester is 100 mass% of electrolyte solution normally, Preferably it is 0.1 mass% or more, More preferably, it is 1 mass% or more. Within this range, the electrical conductivity of the electrolytic solution is improved, and the large current discharge characteristics of the electrolytic solution battery are easily improved. Moreover, the compounding quantity of cyclic carboxylic acid ester becomes like this. Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less. By setting the upper limit in this way, the viscosity of the electrolytic solution is set in an appropriate range, the decrease in electrical conductivity is avoided, the increase in negative electrode resistance is suppressed, and the large current discharge characteristics of the electrolytic solution battery are set in a favorable range. Make it easier.
  • cyclic carboxylic acid ester a fluorinated cyclic carboxylic acid ester (fluorinated lactone) can also be suitably used.
  • fluorine-containing lactone examples include the following formula (C):
  • X 15 to X 20 are the same or different and all are —H, —F, —Cl, —CH 3 or a fluorinated alkyl group; provided that at least one of X 15 to X 20 is a fluorinated alkyl
  • Examples of the fluorinated alkyl group for X 15 to X 20 include —CFH 2 , —CF 2 H, —CF 3 , —CH 2 CF 3 , —CF 2 CF 3 , —CH 2 CF 2 CF 3 , —CF (CF 3 ) 2 and the like are mentioned, and —CH 2 CF 3 and —CH 2 CF 2 CF 3 are preferable from the viewpoint of high oxidation resistance and an effect of improving safety.
  • X 15 to X 20 is a fluorinated alkyl group, —H, —F, —Cl, —CH 3 or the fluorinated alkyl group is substituted at only one position of X 15 to X 20.
  • a plurality of locations may be substituted.
  • it is 1 to 3 sites, more preferably 1 to 2 sites from the viewpoint of good solubility of the electrolyte salt.
  • the substitution position of the fluorinated alkyl group is not particularly limited. However, since the synthesis yield is good, X 17 and / or X 18 is particularly preferably X 17 or X 18 is a fluorinated alkyl group, particularly —CH 2 CF 3. , —CH 2 CF 2 CF 3 is preferable. X 15 to X 20 other than the fluorinated alkyl group are —H, —F, —Cl or CH 3 , and —H is particularly preferable from the viewpoint of good solubility of the electrolyte salt.
  • one of A and B is CX 26 X 27 (X 26 and X 27 are the same or different, and each of them is —H, —F, —Cl, —CF 3 , —CH 3 or a hydrogen atom)
  • Rf 12 is a fluorinated alkyl group or a fluorinated group which may have an ether bond
  • X 21 and X 22 are the same or different; all are —H, —F, —Cl, —CF 3 or CH 3 ;
  • Examples of the chain carboxylic acid ester include those having 3 to 7 carbon atoms in the structural formula. Specifically, methyl acetate, ethyl acetate, acetate n-propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, Isopropyl propionate, n-butyl propionate, isobutyl propionate, t-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, isobutyric acid-n- Examples include propyl and isopropyl isobutyrate.
  • methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, methyl butyrate, ethyl butyrate, etc. are ions due to viscosity reduction. It is preferable from the viewpoint of improvement of conductivity.
  • fluorinated chain carboxylic acid ester can also be used suitably.
  • the fluorine-containing ester the following formula (H): Rf 10 COORf 11 (H) (Wherein Rf 10 is a fluorinated alkyl group having 1 to 2 carbon atoms, Rf 11 is a fluorinated alkyl group having 1 to 4 carbon atoms), and the flame retardant property is high, And it is preferable from the viewpoint of good compatibility with other solvents and oxidation resistance.
  • Rf 10 examples include CF 3- , CF 3 CF 2- , HCF 2 CF 2- , HCF 2- , CH 3 CF 2- , CF 3 CH 2- and the like, among which CF 3- , CF 3 CF 2 -is particularly preferable from the viewpoint of good rate characteristics.
  • Rf 11 examples include —CF 3 , —CF 2 CF 3 , —CH (CF 3 ) 2 , —CH 2 CF 3 , —CH 2 CH 2 CF 3 , —CH 2 CF 2 CFHCF 3 , —CH 2 C 2 F 5 , —CH 2 CF 2 CF 2 H, —CH 2 CH 2 C 2 F 5 , —CH 2 CF 2 CF 3 , —CH 2 CF 2 CF 2 CF 3 and the like can be exemplified, among them —CH 2 CF 3 , —CH (CF 3 ) 2 , —CH 2 C 2 F 5 , and —CH 2 CF 2 CF 2 H are particularly preferable from the viewpoint of good compatibility with other solvents.
  • fluorinated chain carboxylic acid ester examples include, for example, CF 3 C ( ⁇ O) OCH 2 CF 3 , CF 3 C ( ⁇ O) OCH 2 CH 2 CF 3 , and CF 3 C ( ⁇ O) OCH 2 C.
  • CF 3 C ( ⁇ O) OCH 2 CF 3 CF 3 C ( ⁇ O) OCH 2 CH 2 CF 3
  • CF 3 C ( ⁇ O) OCH 2 C One or more of 2 F 5 , CF 3 C ( ⁇ O) OCH 2 CF 2 CF 2 H, CF 3 C ( ⁇ O) OCH (CF 3 ) 2, etc.
  • a chain ether having 3 to 10 carbon atoms and a cyclic ether having 3 to 6 carbon atoms are preferable.
  • the chain ether having 3 to 10 carbon atoms include diethyl ether, di-n-butyl ether, dimethoxymethane, methoxyethoxymethane, diethoxymethane, dimethoxyethane, methoxyethoxyethane, diethoxyethane, and ethylene glycol di-n-propyl.
  • Examples include ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether and the like.
  • a fluorinated ether can also be suitably used.
  • the fluorinated ether include the following general formula (I): Rf 13 -O-Rf 14 (I) (Wherein Rf 13 and Rf 14 are the same or different and are an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms, provided that at least one of Rf 13 and Rf 14 is fluorine.
  • a fluorinated ether (I) represented by formula (1).
  • Rf 13 and Rf 14 may be a fluorinated alkyl group having 1 to 10 carbon atoms.
  • both Rf 13 and Rf 14 are fluorinated alkyl groups having 1 to 10 carbon atoms.
  • Rf 13 and Rf 14 may be the same or different from each other.
  • Rf 13 and Rf 14 are the same or different, Rf 13 is a fluorinated alkyl group having 3 to 6 carbon atoms, and Rf 14 is a fluorinated alkyl group having 2 to 6 carbon atoms. preferable.
  • the fluorinated ether (I) preferably has a fluorine content of 40 to 75% by mass. When it has a fluorine content in this range, it is particularly excellent in the balance between incombustibility and compatibility. Moreover, it is preferable also from a point with favorable oxidation resistance and safety
  • the lower limit of the fluorine content is more preferably 45% by mass, still more preferably 50% by mass, and particularly preferably 55% by mass.
  • the upper limit is more preferably 70% by mass, and still more preferably 66% by mass.
  • the fluorine content of the fluorinated ether (I) is determined based on the structural formula of the fluorinated ether (I): ⁇ (number of fluorine atoms ⁇ 19) / molecular weight of the fluorinated ether (I) ⁇ ⁇ 100 (% ).
  • Rf 13 examples include CF 3 CF 2 CH 2 —, CF 3 CFHCF 2 —, HCF 2 CF 2 CF 2 —, HCF 2 CF 2 CH 2 —, CF 3 CF 2 CH 2 CH 2 —, CF 3 CFHCF 2 CH 2 —, HCF 2 CF 2 CF 2 —, HCF 2 CF 2 CH 2 CH 2 —, HCF 2 CF (CF 3 ) CH 2 — and the like can be mentioned.
  • Rf 14 for example, —CH 2 CF 2 CF 3 , —CF 2 CFHCF 3 , —CF 2 CF 2 CF 2 H, —CH 2 CF 2 CF 2 H, —CH 2 CH 2 CF 2 CF 3 , —CH 2 CF 2 CFHCF 3 , —CF 2 CF 2 CF 2 CF 2 H, —CH 2 CF 2 CF 2 H, —CH 2 CH 2 CF 2 CF 2 H, —CH 2 CF (CF 3 ) CF 2 H, —CF 2 CF 2 H, —CH 2 CF 2 H, —CF 2 CH 3 and the like can be mentioned.
  • fluorinated ether (I) include, for example, HCF 2 CF 2 CH 2 OCF 2 CF 2 H, CF 3 CF 2 CH 2 OCF 2 CF 2 H, HCF 2 CF 2 CH 2 OCF 2 CFHCF 3 , CF 3 CF 2 CH 2 OCF 2 CFHCF 3 , C 6 F 13 OCH 3 , C 6 F 13 OC 2 H 5 , C 8 F 17 OCH 3 , C 8 F 17 OC 2 H 5 , CF 3 CFHCF 2 CH (CH 3 ) OCF 2 CFHCF 3 , HCF 2 CF 2 OCH (C 2 H 5 ) 2 , HCF 2 CF 2 OC 4 H 9 , HCF 2 CF 2 OCH 2 CH (C 2 H 5 ) 2 , HCF 2 CF 2 OCH 2 CH (CH 3) 2 or the like can be mentioned.
  • fluorinated ether (I) having a high boiling point.
  • the boiling point of the fluorinated ether (I) is preferably 67 to 120 ° C. More preferably, it is 80 degreeC or more, More preferably, it is 90 degreeC or more.
  • fluorinated ether (I) examples include CF 3 CH 2 OCF 2 CFHCF 3 , CF 3 CF 2 CH 2 OCF 2 CFHCF 3 , HCF 2 CF 2 CH 2 OCF 2 CFHCF 3 , and HCF 2 CF 2 CH 2 OCH 2 CF 2 CF 2 H , CF 3 CFHCF 2 CH 2 OCF 2 CFHCF 3, HCF 2 CF 2 CH 2 OCF 2 CF 2 H, CF 3 CF 2 CH 2 OCF 2 CF 2 1 type of H, etc. or two The above is mentioned.
  • HCF 2 CF 2 CH 2 OCF 2 CFHCF 3 (boiling point 106 ° C.), CF 3 CF 2 CH is advantageous because of its high boiling point, compatibility with other solvents, and good solubility of the electrolyte salt.
  • 2 OCF 2 CFHCF 3 (boiling point 82 ° C.), HCF 2 CF 2 CH 2 OCF 2 CF 2 H (boiling point 92 ° C.) and CF 3 CF 2 CH 2 OCF 2 CF 2 H (boiling point 68 ° C.).
  • HCF 2 CF 2 CH 2 OCF 2 CFHCF 3 (boiling point 106 ° C.) and HCF 2 CF 2 CH 2 OCF 2 CF 2 H (boiling point 92 ° C.).
  • HCF 2 CF 2 CH 2 OCF 2 CFHCF 3 (boiling point 106 ° C.)
  • HCF 2 CF 2 CH 2 OCF 2 CF 2 H (boiling point 92 ° C.).
  • One type is more preferable.
  • Examples of the cyclic ether having 3 to 6 carbon atoms include 1,3-dioxane, 2-methyl-1,3-dioxane, 4-methyl-1,3-dioxane, 1,4-dioxane, and fluorinated compounds thereof. Is mentioned. Among them, dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol-n-propyl ether, ethylene glycol di-n-butyl ether, and diethylene glycol dimethyl ether have high solvating ability to lithium ions and improve the degree of ion dissociation. Dimethoxymethane, diethoxymethane, and ethoxymethoxymethane are particularly preferable because they have low viscosity and give high ionic conductivity.
  • nitrogen-containing compound examples include nitrile, fluorine-containing nitrile, carboxylic acid amide, fluorine-containing carboxylic acid amide, sulfonic acid amide, and fluorine-containing sulfonic acid amide.
  • 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxaziridinone, 1,3-dimethyl-2-imidazolidinone, N-methylsuccinimide and the like can be used.
  • boron-containing compound examples include boric acid esters such as trimethyl borate and triethyl borate, boric ether, and alkyl borate.
  • organosilicon-containing compound examples include (CH 3 ) 4 —Si, (CH 3 ) 3 —Si—Si (CH 3 ) 3, and the like.
  • Examples of the incombustible (flame retardant) agent include phosphate esters and phosphazene compounds.
  • Examples of the phosphate ester include fluorine-containing alkyl phosphate esters, non-fluorinated alkyl phosphate esters, and aryl phosphate esters. Especially, it is preferable that it is a fluorine-containing alkyl phosphate ester at the point which can exhibit a nonflammable effect in a small quantity.
  • fluorine-containing alkyl phosphate ester examples include fluorine-containing dialkyl phosphate esters described in JP-A No. 11-233141, alkyl phosphate esters described in JP-A No. 11-283669, or And fluorine-containing trialkyl phosphates.
  • nonflammable (flame retardant) agent (CH 3 O) 3 P ⁇ O, (CF 3 CH 2 O) 3 P ⁇ O, and the like are preferable.
  • the surfactant may be any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. From the viewpoint of good cycle characteristics and rate characteristics, a fluorine atom It is preferable that it contains.
  • Rf 15 COO ⁇ M + (J) (In the formula, Rf 15 is a fluorine-containing alkyl group which may contain an ether bond having 3 to 10 carbon atoms; M + is Li + , Na + , K + or NHR ′ 3 + (R ′ is the same or different) Are all H or an alkyl group having 1 to 3 carbon atoms), or a fluorine-containing carboxylate represented by the following formula (K): Rf 16 SO 3 ⁇ M + (K) (In the formula, Rf 16 is a fluorine-containing alkyl group which may contain an ether bond having 3 to 10 carbon atoms; M + is Li + , Na + , K + or NHR ′ 3 + (R ′ is the same or different; These are preferably fluorine-containing sulfonates represented by the following formula: H or an alkyl group having 1 to 3 carbon atoms;
  • the content of the surfactant is preferably 0.01 to 2% by mass in the electrolytic solution from the viewpoint that the surface tension of the electrolytic solution can be reduced without reducing the charge / discharge cycle characteristics.
  • high dielectric additive examples include sulfolane, methyl sulfolane, ⁇ -butyrolactone, ⁇ -valerolactone, acetonitrile, propionitrile and the like.
  • cycle characteristic and rate characteristic improving agent examples include methyl acetate, ethyl acetate, tetrahydrofuran, 1,4-dioxane and the like.
  • the overcharge preventing agent is preferably an overcharge preventing agent having an aromatic ring in that the battery can be prevented from being ruptured or ignited during overcharging.
  • the overcharge preventing agent having an aromatic ring include cyclohexylbenzene, biphenyl, alkylbiphenyl, terphenyl, terphenyl partial hydride, t-butylbenzene, t-amylbenzene, diphenyl ether, benzofuran, dibenzofuran, dichloroaniline.
  • Aromatic compounds such as toluene, fluorinated aromatic compounds such as hexafluorobenzene, fluorobenzene, 2-fluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5 -Fluorinated anisole compounds such as difluoroanisole, 2,6-difluoroanisole, and 3,5-difluoroanisole.
  • aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, terphenyl partially hydrogenated, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran are preferable. These may be used alone or in combination of two or more.
  • the content of the overcharge inhibitor is preferably 0.1 to 5% by mass in the electrolytic solution from the viewpoint that the battery can be prevented from bursting or firing in the case of overcharging or the like.
  • the electrolyte solution may further contain other known auxiliaries as long as the performance as the electrolyte solution is not impaired.
  • auxiliary agents include carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, Carboxylic anhydrides such as glutaconic anhydride, itaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride and phenylsuccinic anhydride; 2,4,8,10-tetraoxa Spiro compounds such as spiro [5,5] undecane and 3,9-divinyl-2,4,8,10-tetraoxaspiro [5,5] undecane; ethylene sulfite, methyl fluorosulf
  • electrolyte solution may be further combined with a polymer material to form a gel (plasticized) gel electrolyte solution.
  • Examples of such a polymer material include conventionally known polyethylene oxide and polypropylene oxide, modified products thereof (JP-A-8-222270 and JP-A-2002-1000040); polyacrylate polymers, polyacrylonitrile, and polyvinylidene fluoride.
  • Fluorine resins such as vinylidene fluoride-hexafluoropropylene copolymer (JP-A-4-506726, JP-A-8-507407, JP-A-10-294131); Examples include composites with resins (Japanese Patent Laid-Open Nos. 11-35765 and 11-86630).
  • the electrolytic solution may also contain an ion conductive compound described in Japanese Patent Application No. 2004-301934.
  • This ion conductive compound has the formula (1-1): A- (D) -B (1-1) [Wherein D represents the formula (2-1a): -(D1) n- (FAE) m- (AE) p- (Y) q- (2-1a) (In the formula, D1 represents the formula (2a):
  • Rf is a fluorine-containing ether group which may have a crosslinkable functional group; the R 10 group or a bond that binds the Rf main chain
  • ether having a fluorine-containing ether group in the side chain represented by unit FAE is represented by formula (2b):
  • Rfa is hydrogen atom, a crosslinkable functional group which may have a fluorinated alkyl group; R 11 is a group or a bond that binds the Rfa main chain) fluorinated alkyl group in the side chain represented by Ether units having: AE is the formula (2c):
  • R 13 has a hydrogen atom, an alkyl group which may have a crosslinkable functional group, an aliphatic cyclic hydrocarbon group which may have a crosslinkable functional group, or a crosslinkable functional group.
  • An aromatic hydrocarbon group which may be present R 12 is an ether unit represented by R 13 and a group or a bond which bonds the main chain;
  • Y represents the formulas (2d-1) to (2d-3):
  • a and B are the same or different and are a hydrogen atom, a fluorine atom and / or an alkyl group which may contain a crosslinkable functional group, a fluorine atom and / or a phenyl group which may contain a crosslinkable functional group, —COOH A group, —OR (wherein R is a hydrogen atom or a fluorine atom and / or an alkyl group which may contain a crosslinkable functional group), an ester group or a carbonate group (provided that when D is terminated with an oxygen atom, a —COOH group;
  • the electrolytic solution may be prepared by any method using the above-described components.
  • the electrolytic solution can be suitably applied to electrochemical devices such as secondary batteries.
  • the electrochemical device include lithium ion secondary batteries, capacitors (electric double layer capacitors), radical batteries, solar cells (particularly dye-sensitized solar cells), fuel cells, various electrochemical sensors, electrochromic elements, electrochemical A switching element, an aluminum electrolytic capacitor, a tantalum electrolytic capacitor, etc. are mentioned, A lithium ion secondary battery and an electric double layer capacitor are suitable.
  • a lithium ion secondary battery is demonstrated as an example of the said electrochemical device or a secondary battery.
  • the lithium ion secondary battery includes a positive electrode, a negative electrode, and the above-described electrolytic solution.
  • a positive electrode is comprised from the positive electrode mixture containing the positive electrode active material which is a material of a positive electrode, and a collector.
  • the positive electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions.
  • a material containing lithium and at least one transition metal is preferable.
  • Specific examples include lithium-containing transition metal composite oxides and lithium-containing transition metal phosphate compounds.
  • the lithium containing transition metal complex oxide which produces a high voltage is especially preferable.
  • lithium-containing transition metal composite oxide examples include: Formula (L): Li a Mn 2-b M 1 b O 4 (where 0.9 ⁇ a; 0 ⁇ b ⁇ 1.5; M 1 is Fe, Co, Ni, Cu, Zn, Al, Sn) , Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge, at least one metal selected from the group consisting of lithium and manganese spinel composite oxides, Formula (M): LiNi 1-c M 2 c O 2 (where 0 ⁇ c ⁇ 0.5; M 2 is Fe, Co, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg) , At least one metal selected from the group consisting of Ca, Sr, B, Ga, In, Si and Ge), or Formula (N): LiCo 1-d M 3 d O 2 (where 0 ⁇ d ⁇ 0.5; M 3 is Fe, Ni, Mn, Cu, Zn, Al, Sn, Cr, V,
  • LiCoO 2 , LiMnO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi 0.8 Co 0.15 Al 0.05 O 2 can be provided because the lithium ion secondary battery with high energy density and high output can be provided. Or LiNi 1/3 Co 1/3 Mn 1/3 O 2 is preferred.
  • LiFePO 4 LiNi 0.8 Co 0.2 O 2 , Li 1.2 Fe 0.4 Mn 0.4 O 2 , LiNi 0.5 Mn 0.5 O 2 , LiV 3 O 6 etc. are mentioned.
  • lithium phosphate in the positive electrode active material because continuous charge characteristics are improved.
  • the lower limit of the amount of lithium phosphate to be used is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass with respect to the total of the positive electrode active material and lithium phosphate. %, And the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate, and carbon.
  • these surface adhering substances are dissolved or suspended in a solvent, impregnated and added to the positive electrode active material, and dried.
  • the surface adhering substance precursor is dissolved or suspended in a solvent and impregnated and added to the positive electrode active material, It can be made to adhere to the surface of the positive electrode active material by a method of reacting by heating or the like, a method of adding to the positive electrode active material precursor and firing simultaneously.
  • the method of making carbonaceous adhere mechanically later in the form of activated carbon etc. can also be used, for example.
  • the amount of the surface adhering substance is, in terms of mass with respect to the positive electrode active material, preferably 0.1 ppm or more, more preferably 1 ppm or more, further preferably 10 ppm or more, and the upper limit, preferably 20% or less, more preferably as the lower limit. Is used at 10% or less, more preferably 5% or less.
  • the surface adhering substance can suppress the oxidation reaction of the electrolyte solution on the surface of the positive electrode active material and can improve the battery life. However, when the amount of the adhering quantity is too small, the effect is not sufficiently manifested. If it is too high, the resistance may increase in order to inhibit the entry and exit of lithium ions.
  • Examples of the shape of the particles of the positive electrode active material include a lump shape, a polyhedron shape, a sphere shape, an oval sphere shape, a plate shape, a needle shape, and a column shape as conventionally used. Moreover, primary particles may aggregate to form secondary particles.
  • the tap density of the positive electrode active material is preferably 0.5 g / cm 3 or more, more preferably 0.8 g / cm 3 or more, and further preferably 1.0 g / cm 3 or more. If the tap density of the positive electrode active material is lower than the lower limit, the amount of the required dispersion medium increases when the positive electrode active material layer is formed, and the necessary amount of conductive material and binder increases, so that the positive electrode to the positive electrode active material layer The filling rate of the active material is restricted, and the battery capacity may be restricted. By using a complex oxide powder having a high tap density, a high-density positive electrode active material layer can be formed.
  • the tap density is preferably as large as possible, and there is no particular upper limit, but if it is too large, diffusion of lithium ions using the electrolytic solution in the positive electrode active material layer as a medium is rate-limiting, and load characteristics may be easily reduced.
  • the upper limit is preferably 4.0 g / cm 3 or less, more preferably 3.7 g / cm 3 or less, and still more preferably 3.5 g / cm 3 or less.
  • the tap density is determined as powder packing density (tap density) g / cm 3 when 5 to 10 g of the positive electrode active material powder is put in a 10 ml glass graduated cylinder and tapped 200 times with a stroke of about 20 mm.
  • the median diameter d50 of the positive electrode active material particles is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably. Is 0.8 ⁇ m or more, most preferably 1.0 ⁇ m or more, preferably 30 ⁇ m or less, more preferably 27 ⁇ m or less, further preferably 25 ⁇ m or less, and most preferably 22 ⁇ m or less. If the lower limit is not reached, a high tap density product may not be obtained. If the upper limit is exceeded, it takes time for the diffusion of lithium in the particles, resulting in a decrease in battery performance or production of the positive electrode of the battery, that is, an active material.
  • the median diameter d50 is measured by a known laser diffraction / scattering particle size distribution measuring device.
  • LA-920 manufactured by HORIBA is used as a particle size distribution meter
  • a 0.1% by mass sodium hexametaphosphate aqueous solution is used as a dispersion medium for measurement, and a measurement refractive index of 1.24 is set after ultrasonic dispersion for 5 minutes. Measured.
  • the average primary particle diameter of the positive electrode active material is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and still more preferably 0.8.
  • the upper limit is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3 ⁇ m or less, and most preferably 2 ⁇ m or less. If the above upper limit is exceeded, it is difficult to form spherical secondary particles, which adversely affects the powder filling property, or the specific surface area is greatly reduced, so that there is a high possibility that battery performance such as output characteristics will deteriorate. is there. On the other hand, when the value falls below the lower limit, there is a case where problems such as inferior reversibility of charge / discharge are usually caused because crystals are not developed.
  • the primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph at a magnification of 10000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is obtained for any 50 primary particles and obtained by taking the average value. It is done.
  • SEM scanning electron microscope
  • BET specific surface area of the positive electrode active material is preferably 0.1 m 2 / g or more, more preferably 0.2 m 2 / g or more, still more preferably 0.3 m 2 / g or more, and preferably 50 m 2 / g or less, more preferably 40 m 2 / g or less, and further preferably 30 m 2 / g or less. If the BET specific surface area is smaller than this range, the battery performance tends to be lowered. If the BET specific surface area is larger, the tap density is difficult to increase, and a problem may occur in applicability when forming the positive electrode active material layer.
  • the BET specific surface area was measured by preliminarily drying the sample at 150 ° C. for 30 minutes under a nitrogen flow using a surface area meter (for example, a fully automatic surface area measuring device manufactured by Okura Riken Co., Ltd.), It is defined by a value measured by a nitrogen adsorption BET one-point method using a gas flow method using a nitrogen helium mixed gas that is accurately adjusted so that the relative pressure value is 0.3.
  • a surface area meter for example, a fully automatic surface area measuring device manufactured by Okura Riken Co., Ltd.
  • the positive electrode active material particles are mainly secondary particles. It is preferable.
  • the particles of the positive electrode active material preferably contain 0.5 to 7.0% by volume of fine particles having an average secondary particle size of 40 ⁇ m or less and an average primary particle size of 1 ⁇ m or less. By containing fine particles having an average primary particle size of 1 ⁇ m or less, the contact area with the electrolytic solution is increased, and the diffusion of lithium ions between the electrode and the electrolytic solution can be further accelerated. Output performance can be improved.
  • a general method is used as a manufacturing method of the inorganic compound.
  • various methods are conceivable for preparing a spherical or elliptical active material.
  • a transition metal source material is dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring.
  • a spherical precursor is prepared and recovered, and dried as necessary.
  • a Li source such as LiOH, Li 2 CO 3 , LiNO 3 is added, and the active material is obtained by baking at a high temperature. .
  • the positive electrode active material may be used alone, or one or more of different compositions may be used in any combination or ratio.
  • a preferable combination in this case is a combination of LiCoO 2 and LiMn 2 O 4 such as LiNi 0.33 Co 0.33 Mn 0.33 O 2 or a part of this Mn substituted with another transition metal or the like. Or a combination with LiCoO 2 or a part of this Co substituted with another transition metal or the like.
  • the content of the positive electrode active material is preferably 50 to 99% by mass, more preferably 80 to 99% by mass of the positive electrode mixture, from the viewpoint of high battery capacity.
  • the content of the positive electrode active material in the positive electrode active material layer is preferably 80% by mass or more, more preferably 82% by mass or more, and particularly preferably 84% by mass or more. Moreover, Preferably it is 99 mass% or less, More preferably, it is 98 mass% or less. If the content of the positive electrode active material in the positive electrode active material layer is low, the electric capacity may be insufficient. Conversely, if the content is too high, the strength of the positive electrode may be insufficient.
  • the positive electrode mixture preferably further contains a binder, a thickener, and a conductive material.
  • a binder any material can be used as long as it is a material that is safe with respect to the solvent and the electrolyte used in the production of the electrode.
  • polyvinylidene fluoride polytetrafluoroethylene, polyethylene, polypropylene , SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, nitrocellulose, NBR (Acrylonitrile-butadiene rubber), fluoro rubber, ethylene-propylene rubber, styrene / butadiene / styrene block copolymer or its hydrogenated product, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / Tadiene / ethylene copolymer, styrene / isoprene / styrene block copolymer or hydrogenated product thereof, syndiotact
  • the content of the binder is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, as a ratio of the binder in the positive electrode active material layer. Usually, it is 80 mass% or less, Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less, Most preferably, it is 10 mass% or less.
  • the ratio of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. On the other hand, if it is too high, battery capacity and conductivity may be reduced.
  • thickener examples include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. 1 type may be used independently or 2 or more types may be used together by arbitrary combinations and a ratio.
  • the ratio of the thickener to the active material is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and usually 5% by mass or less, preferably 3%. It is in the range of not more than mass%, more preferably not more than 2 mass%. Below this range, applicability may be significantly reduced. If it exceeds, the ratio of the active material in the positive electrode active material layer may decrease, and there may be a problem that the capacity of the battery decreases and a problem that the resistance between the positive electrode active materials increases.
  • a known conductive material can be arbitrarily used as the conductive material.
  • Specific examples include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite; carbon black such as acetylene black; and carbon materials such as amorphous carbon such as needle coke. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the conductive material is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass in the positive electrode active material layer. % Or less, more preferably 15% by mass or less. If the content is lower than this range, the conductivity may be insufficient. Conversely, if the content is higher than this range, the battery capacity may decrease.
  • the solvent for forming the slurry the positive electrode active material, the conductive material, the binder, and a solvent capable of dissolving or dispersing the thickener used as necessary may be used.
  • an aqueous solvent or an organic solvent may be used.
  • the aqueous medium include water, a mixed medium of alcohol and water, and the like.
  • the organic medium include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone.
  • Esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N, N-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) Amides such as dimethylformamide and dimethylacetamide; and aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.
  • amines such as diethylenetriamine and N, N-dimethylaminopropylamine
  • ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF)
  • NMP N-methylpyrrolidone
  • Amides such as dimethylformamide and dimethylacetamide
  • aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.
  • Examples of the material for the positive electrode current collector include metals such as aluminum, titanium, tantalum, stainless steel, and nickel, or metal materials such as alloys thereof; carbon materials such as carbon cloth and carbon paper. Among these, a metal material, particularly aluminum or an alloy thereof is preferable.
  • Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal in the case of a metal material.
  • a thin film, a carbon cylinder, etc. are mentioned. Of these, metal thin films are preferred.
  • the thickness of the thin film is arbitrary, but is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and usually 1 mm or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less. If the thin film is thinner than this range, the strength required for the current collector may be insufficient. Conversely, if the thin film is thicker than this range, the handleability may be impaired.
  • a conductive additive is applied to the surface of the current collector.
  • the conductive assistant include noble metals such as carbon, gold, platinum, and silver.
  • the ratio of the thickness of the current collector to the positive electrode active material layer is not particularly limited, but the value of (thickness of the positive electrode active material layer on one side immediately before electrolyte injection) / (thickness of the current collector) is 20 Is preferably 15 or less, most preferably 10 or less, and preferably 0.5 or more, more preferably 0.8 or more, and most preferably 1 or more. Above this range, the current collector may generate heat due to Joule heat during high current density charge / discharge. Below this range, the volume ratio of the current collector to the positive electrode active material increases and the battery capacity may decrease.
  • the positive electrode may be manufactured by a conventional method.
  • the above-mentioned positive electrode active material is added with the above-mentioned binder, thickener, conductive material, solvent, etc. to form a slurry-like positive electrode mixture, which is applied to a current collector, dried and then pressed.
  • a method of densification is mentioned.
  • the densification can be performed by a hand press, a roller press or the like.
  • the density of the positive electrode active material layer is preferably 1.5 g / cm 3 or more, more preferably 2 g / cm 3 or more, still more preferably 2.2 g / cm 3 or more, and preferably 5 g / cm 3 or less. More preferably, it is 4.5 g / cm ⁇ 3 > or less, More preferably, it is the range of 4 g / cm ⁇ 3 > or less. If it exceeds this range, the permeability of the electrolyte solution to the vicinity of the current collector / active material interface decreases, and the charge / discharge characteristics particularly at a high current density decrease, and a high output may not be obtained. On the other hand, if it is lower, the conductivity between the active materials is lowered, the battery resistance is increased, and a high output may not be obtained.
  • the sum of the electrode areas of the positive electrode with respect to the surface area of the exterior of the secondary battery is preferably 15 times or more, and more preferably 40 times or more.
  • the outer surface area of the battery outer case in the case of a square shape with a bottom, is the total area calculated from the vertical, horizontal, and thickness dimensions of the case part filled with the power generation element excluding the protruding part of the terminal.
  • the geometric surface area approximates the case portion filled with the power generation element excluding the protruding portion of the terminal as a cylinder.
  • the total electrode area of the positive electrode is the geometric surface area of the positive electrode mixture layer facing the mixture layer containing the negative electrode active material. , The sum of the areas where each surface is calculated separately.
  • the thickness of the positive electrode plate is not particularly limited, but from the viewpoint of high capacity and high output, the thickness of the composite layer obtained by subtracting the metal foil thickness of the core material is preferably as a lower limit with respect to one side of the current collector. Is 10 ⁇ m or more, more preferably 20 ⁇ m or more, and preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate, and carbon.
  • the negative electrode is composed of a negative electrode mixture containing a negative electrode active material and a current collector.
  • Examples of the negative electrode active material include carbonaceous materials capable of occluding and releasing lithium, such as organic pyrolysis products and artificial graphite and natural graphite under various pyrolysis conditions; occluding and releasing lithium such as tin oxide and silicon oxide. Possible metal oxide materials; lithium metal; various lithium alloys; lithium-containing metal composite oxide materials. These negative electrode active materials may be used in combination of two or more.
  • artificial graphite or purified natural graphite produced by high-temperature treatment of graphitizable pitch obtained from various raw materials, or surface treatment with pitch or other organic substances on these graphites
  • carbonized material obtained by carbonizing natural graphite, artificial graphite, artificial carbonaceous material, and artificial graphite material at least once in the range of 400 to 3200 ° C., and a negative electrode active material layer.
  • a carbonaceous material comprising at least two kinds of carbonaceous materials having different crystallinity and / or having an interface in contact with the different crystalline carbonaceous materials, and at least two kinds of different orientations of the negative electrode active material layer
  • a carbonaceous material having an interface with which the carbonaceous material is in contact is more preferable because of a good balance between initial irreversible capacity and high current density charge / discharge characteristics.
  • these carbon materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • Carbonaceous materials obtained by heat-treating the above-mentioned artificial carbonaceous materials and artificial graphite materials at least once in the range of 400 to 3200 ° C include coal-based coke, petroleum-based coke, coal-based pitch, petroleum-based pitch, and oxidation of these pitches.
  • Treated, needle coke, pitch coke and partially carbonized carbon agents, furnace black, acetylene black, pyrolytic products of organic materials such as pitch-based carbon fibers, carbonizable organic materials and their carbides, or carbonizable Examples thereof include solutions obtained by dissolving organic substances in low molecular organic solvents such as benzene, toluene, xylene, quinoline, n-hexane, and carbides thereof.
  • the metal material used as the negative electrode active material excluding lithium-titanium composite oxide
  • simple lithium, simple metal and alloy forming lithium alloy or oxidation thereof
  • Any of compounds such as oxides, carbides, nitrides, silicides, sulfides or phosphides may be used, and there is no particular limitation.
  • the single metal and alloy forming the lithium alloy are preferably materials containing group 13 and group 14 metal / metalloid elements, more preferably aluminum, silicon and tin (hereinafter abbreviated as “specific metal elements”). ) Simple metals and alloys or compounds containing these atoms. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • a negative electrode active material having at least one kind of atom selected from a specific metal element, a metal simple substance of any one specific metal element, an alloy composed of two or more specific metal elements, one type or two or more specific types Alloys comprising metal elements and one or more other metal elements, as well as compounds containing one or more specific metal elements, and oxides, carbides, nitrides and silicides of the compounds And composite compounds such as sulfides or phosphides.
  • these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.
  • a compound in which these complex compounds are complexly bonded to several kinds of elements such as a simple metal, an alloy, or a nonmetallic element is also included.
  • a simple metal, an alloy, or a nonmetallic element such as silicon and tin
  • an alloy of these elements and a metal that does not operate as a negative electrode can be used.
  • a complex compound containing 5 to 6 kinds of elements in combination with a metal that acts as a negative electrode other than tin and silicon, a metal that does not operate as a negative electrode, and a nonmetallic element may be used. it can.
  • a composite material including Si or Sn as the first constituent element and the second and third constituent elements in addition thereto can be given.
  • the second constituent element is, for example, at least one of cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium, and zirconium.
  • the third constituent element is at least one of boron, carbon, aluminum, and phosphorus.
  • the metal material silicon or tin alone (which may contain a small amount of impurities), SiOv (0 ⁇ v ⁇ 2), SnOw (0 ⁇ w) ⁇ 2), Si—Co—C composite material, Si—Ni—C composite material, Sn—Co—C composite material, and Sn—Ni—C composite material are preferable.
  • the lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as it can occlude and release lithium, but a material containing titanium and lithium is preferable from the viewpoint of high current density charge / discharge characteristics, A lithium-containing composite metal oxide material containing titanium is more preferable, and a composite oxide of lithium and titanium (hereinafter abbreviated as “lithium titanium composite oxide”) is more preferable. That is, it is particularly preferable to use a lithium-titanium composite oxide having a spinel structure in a negative electrode active material for an electrolyte battery because the output resistance is greatly reduced.
  • lithium titanium complex oxide general formula (O): Li x Ti y M z O 4 (O) [In the general formula (O), M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb. ] It is preferable that it is a compound represented by these.
  • This structure is particularly preferable because of a good balance of battery performance.
  • compositions of the above compounds are Li 4/3 Ti 5/3 O 4 in (i), Li 1 Ti 2 O 4 in (ii), and Li 4/5 Ti 11/5 O in (iii). 4 .
  • structure of Z ⁇ 0, for example, Li 4/3 Ti 4/3 Al 1/3 O 4 is preferable.
  • the negative electrode mixture preferably further contains a binder, a thickener, and a conductive material.
  • the ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.6% by mass or more, and preferably 20% by mass or less. It is more preferably at most 10 mass%, further preferably at most 10 mass%, particularly preferably at most 8 mass%.
  • the ratio of the binder to the negative electrode active material exceeds the above range, the binder ratio in which the amount of the binder does not contribute to the battery capacity increases, and the battery capacity may be reduced.
  • the strength of the negative electrode may be reduced.
  • the ratio of the binder to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more. 0.6 mass% or more is more preferable, and is usually 5 mass% or less, preferably 3 mass% or less, and more preferably 2 mass% or less.
  • the ratio to the negative electrode active material is usually 1% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more. It is preferably 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less.
  • the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and usually 5% by mass or less. 3 mass% or less is preferable and 2 mass% or less is more preferable.
  • the ratio of the thickener to the negative electrode active material is less than the above range, applicability may be significantly reduced.
  • it exceeds the said range the ratio of the negative electrode active material which occupies for a negative electrode active material layer will fall, and the problem that the capacity
  • Examples of the conductive material for the negative electrode include metal materials such as copper and nickel; carbon materials such as graphite and carbon black.
  • the solvent for forming the slurry As the solvent for forming the slurry, the negative electrode active material, the binder, and the thickener and conductive material used as necessary can be dissolved or dispersed as long as it is a solvent. There is no restriction, and either an aqueous solvent or an organic solvent may be used. Examples of the aqueous solvent include water and alcohol.
  • organic solvent examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N- Examples include dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, diethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane, and the like.
  • NMP N-methylpyrrolidone
  • dimethylformamide dimethylacetamide
  • methyl ethyl ketone cyclohexanone
  • methyl acetate methyl acrylate
  • diethyltriamine N
  • N- Examples include dimethylaminopropylamine, tetrahydr
  • Examples of the material for the negative electrode current collector include copper, nickel, and stainless steel. Among these, copper is preferable from the viewpoint of easy processing into a thin film and cost.
  • the thickness of the current collector is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, and is usually 100 ⁇ m or less, preferably 50 ⁇ m or less. If the thickness of the negative electrode current collector is too thick, the capacity of the entire battery may be reduced too much, and conversely if it is too thin, handling may be difficult.
  • the negative electrode may be manufactured by a conventional method.
  • the above-described negative electrode material is added with the above-mentioned binder, thickener, conductive material, solvent, etc. to form a slurry, which is applied to a current collector, dried, pressed and densified.
  • a method of forming the above-described thin film layer (negative electrode active material layer) containing the negative electrode active material by a technique such as vapor deposition, sputtering, or plating is also used.
  • the electrode structure when the negative electrode active material is made into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is preferably 1 g ⁇ cm ⁇ 3 or more, and 1.2 g ⁇ cm ⁇ 3 or more. but more preferably, particularly preferably 1.3 g ⁇ cm -3 or more, preferably 2.2 g ⁇ cm -3 or less, more preferably 2.1 g ⁇ cm -3 or less, 2.0 g ⁇ cm -3 or less More preferred is 1.9 g ⁇ cm ⁇ 3 or less.
  • the density of the negative electrode active material present on the current collector exceeds the above range, the negative electrode active material particles are destroyed, increasing the initial irreversible capacity, or the electrolyte solution near the current collector / negative electrode active material interface In some cases, high current density charge / discharge characteristics are deteriorated due to a decrease in permeability.
  • the amount is less than the above range, the conductivity between the negative electrode active materials decreases, the battery resistance increases, and the capacity per unit volume may decrease.
  • the thickness of the negative electrode plate is designed according to the positive electrode plate to be used, and is not particularly limited.
  • the thickness of the composite layer obtained by subtracting the thickness of the metal foil of the core is usually 15 ⁇ m or more, preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more, and usually 300 ⁇ m or less, preferably 280 ⁇ m or less, more preferably 250 ⁇ m or less.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.
  • the lithium ion secondary battery preferably further includes a separator.
  • the material and shape of the separator are not particularly limited as long as they are stable to the electrolytic solution and excellent in liquid retention, and known ones can be used. Among these, it is preferable to use a resin, glass fiber, inorganic material, or the like formed of a material that is stable with respect to the electrolytic solution, and use a porous sheet or a non-woven fabric in which liquid retention is excellent.
  • polyolefins such as polyethylene and polypropylene, aromatic polyamides, polytetrafluoroethylene, polyethersulfone, glass filters and the like can be used. These materials, such as a polypropylene / polyethylene two-layer film and a polypropylene / polyethylene / polypropylene three-layer film, may be used alone or in combination of two or more in any combination and ratio.
  • the said separator is the porous sheet
  • the thickness of the separator is arbitrary, but is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and usually 50 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less. If the separator is too thin than the above range, the insulating properties and mechanical strength may decrease. On the other hand, if it is thicker than the above range, not only battery performance such as rate characteristics may be lowered, but also the energy density of the entire electrolyte battery may be lowered.
  • the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Further, it is usually 90% or less, preferably 85% or less, and more preferably 75% or less. If the porosity is too smaller than the above range, the membrane resistance tends to increase and the rate characteristics tend to deteriorate. Moreover, when larger than the said range, it exists in the tendency for the mechanical strength of a separator to fall and for insulation to fall.
  • the average pore diameter of a separator is also arbitrary, it is 0.5 micrometer or less normally, 0.2 micrometer or less is preferable, and it is 0.05 micrometer or more normally. If the average pore diameter exceeds the above range, a short circuit tends to occur. On the other hand, below the above range, the film resistance may increase and the rate characteristics may deteriorate.
  • oxides such as alumina and silicon dioxide
  • nitrides such as aluminum nitride and silicon nitride
  • sulfates such as barium sulfate and calcium sulfate are used. Used.
  • a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used.
  • the thin film shape those having a pore diameter of 0.01 to 1 ⁇ m and a thickness of 5 to 50 ⁇ m are preferably used.
  • a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used.
  • a porous layer may be formed by using alumina particles having a 90% particle size of less than 1 ⁇ m on both surfaces of the positive electrode and using a fluororesin as a binder.
  • the electrode group has a laminated structure in which the positive electrode plate and the negative electrode plate are interposed through the separator, and a structure in which the positive electrode plate and the negative electrode plate are wound in a spiral shape through the separator. Either is acceptable.
  • the ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group occupation ratio) is usually 40% or more, preferably 50% or more, and usually 90% or less, preferably 80% or less. .
  • the battery capacity decreases. Also, if the above range is exceeded, the void space is small, the battery expands, and the member expands or the vapor pressure of the electrolyte liquid component increases and the internal pressure rises. In some cases, the gas release valve that lowers various characteristics such as storage at high temperature and the like, or releases the internal pressure to the outside is activated.
  • the current collecting structure is not particularly limited, but in order to more effectively realize the high current density charge / discharge characteristics by the electrolytic solution, it is preferable to have a structure in which the resistance of the wiring portion and the joint portion is reduced. Thus, when internal resistance is reduced, the effect of using the said electrolyte solution is exhibited especially favorable.
  • the electrode group has the above laminated structure
  • a structure formed by bundling the metal core portions of the electrode layers and welding them to the terminals is preferably used.
  • the internal resistance increases. Therefore, it is also preferable to provide a plurality of terminals in the electrode to reduce the resistance.
  • the electrode group has the winding structure described above, the internal resistance can be lowered by providing a plurality of lead structures for the positive electrode and the negative electrode, respectively, and bundling the terminals.
  • the material of the outer case is not particularly limited as long as it is a material that is stable with respect to the electrolytic solution used. Specifically, a nickel-plated steel plate, stainless steel, aluminum, an aluminum alloy, a metal such as a magnesium alloy, or a laminated film (laminate film) of a resin and an aluminum foil is used. From the viewpoint of weight reduction, an aluminum or aluminum alloy metal or a laminate film is preferably used.
  • the metal is welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed sealed structure, or a caulking structure using the above metals via a resin gasket. Things.
  • the outer case using the laminate film include a case where a resin-sealed structure is formed by heat-sealing resin layers.
  • a resin different from the resin used for the laminate film may be interposed between the resin layers.
  • a resin layer is heat-sealed through a current collecting terminal to form a sealed structure, a metal and a resin are joined, so that a resin having a polar group or a modified group having a polar group introduced as an intervening resin is used.
  • Resins are preferably used.
  • the shape of the lithium ion secondary battery is arbitrary, and examples thereof include a cylindrical shape, a square shape, a laminate shape, a coin shape, and a large shape.
  • the shape and structure of a positive electrode, a negative electrode, and a separator can be changed and used according to the shape of each battery.
  • An electrochemical device or secondary battery comprising the above electrolyte can be suitably used for a module. It is preferable that the module includes an electrochemical device or a secondary battery including the electrolytic solution.
  • an electric double layer capacitor can be given.
  • the electric double layer capacitor at least one of the positive electrode and the negative electrode is a polarizable electrode, and the following electrodes described in detail in JP-A-9-7896 can be used as the polarizable electrode and the nonpolarizable electrode.
  • the polarizable electrode mainly composed of activated carbon preferably contains non-activated carbon having a large specific surface area and a conductive agent such as carbon black imparting electron conductivity.
  • the polarizable electrode can be formed by various methods.
  • a polarizable electrode made of activated carbon and carbon black can be formed by mixing activated carbon powder, carbon black, and a phenolic resin, and firing and activating in an inert gas atmosphere and a water vapor atmosphere after press molding.
  • the polarizable electrode is joined to the current collector with a conductive adhesive or the like.
  • activated carbon powder, carbon black, and a binder can be kneaded in the presence of alcohol, formed into a sheet, and dried to form a polarizable electrode.
  • a polarizable electrode For example, polytetrafluoroethylene is used as the binder.
  • activated carbon powder, carbon black, binder and solvent are mixed to form a slurry, and this slurry is coated on the metal foil of the current collector and dried to obtain a polarizable electrode integrated with the current collector. it can.
  • An electric double layer capacitor may be formed by using a polarizable electrode mainly composed of activated carbon for both electrodes, but a configuration using a non-polarizable electrode on one side, for example, a positive electrode mainly composed of a battery active material such as a metal oxide, and activated carbon
  • a positive electrode mainly composed of a battery active material such as a metal oxide such as a metal oxide
  • activated carbon A structure combining a polarizable electrode negative electrode mainly composed of carbon, a negative electrode mainly composed of a carbon material capable of reversibly occluding and releasing lithium ions, or a negative electrode composed mainly of lithium metal or lithium alloy and activated carbon.
  • a combination with a polar electrode is also possible.
  • carbonaceous materials such as carbon black, graphite, expanded graphite, porous carbon, carbon nanotube, carbon nanohorn, and ketjen black may be used instead of or in combination with activated carbon.
  • the non-polarizable electrode is preferably composed mainly of a carbon material capable of reversibly occluding and releasing lithium ions, and an electrode obtained by occluding lithium ions in this carbon material is used for the electrode.
  • a lithium salt is used as the electrolyte. According to the electric double layer capacitor having this configuration, a higher withstand voltage exceeding 4 V can be obtained.
  • Solvents used to prepare the slurry for electrode preparation are preferably those that dissolve the binder.
  • Dimethyl acid, ethanol, methanol, butanol or water is appropriately selected.
  • Examples of the activated carbon used for the polarizable electrode include phenol resin-based activated carbon, coconut-based activated carbon, and petroleum coke-based activated carbon. Among these, it is preferable to use petroleum coke activated carbon or phenol resin activated carbon in that a large capacity can be obtained.
  • Activated carbon activation treatment methods include a steam activation treatment method, a molten KOH activation treatment method, and the like, and it is preferable to use activated carbon obtained by a molten KOH activation treatment method in terms of obtaining a larger capacity.
  • Preferred conductive agents used for the polarizable electrode include carbon black, ketjen black, acetylene black, natural graphite, artificial graphite, metal fiber, conductive titanium oxide, and ruthenium oxide.
  • the mixing amount of the conductive agent such as carbon black used for the polarizable electrode is so as to obtain good conductivity (low internal resistance), and if it is too large, the product capacity is reduced. It is preferable to set it as 50 mass%.
  • activated carbon As the activated carbon used for the polarizable electrode, activated carbon having an average particle size of 20 ⁇ m or less and a specific surface area of 1500 to 3000 m 2 / g is used so that an electric double layer capacitor having a large capacity and a low internal resistance can be obtained. Is preferred.
  • a preferable carbon material for constituting an electrode mainly composed of a carbon material capable of reversibly inserting and extracting lithium ions natural graphite, artificial graphite, graphitized mesocarbon spherule, graphitized whisker, gas layer Examples thereof include a grown carbon fiber, a fired product of furfuryl alcohol resin, and a fired product of novolac resin.
  • the current collector is only required to be chemically and electrochemically corrosion resistant.
  • As the current collector of the polarizable electrode mainly composed of activated carbon stainless steel, aluminum, titanium or tantalum can be preferably used. Of these, stainless steel or aluminum is a particularly preferable material in terms of both characteristics and cost of the obtained electric double layer capacitor.
  • As the current collector of the electrode mainly composed of a carbon material capable of reversibly inserting and extracting lithium ions stainless steel, copper or nickel is preferably used.
  • lithium ions in order to preliminarily store lithium ions in a carbon material capable of reversibly inserting and extracting lithium ions, (1) mixing powdered lithium with a carbon material capable of reversibly inserting and extracting lithium ions. (2) A lithium foil is placed on an electrode formed of a carbon material capable of reversibly occluding and releasing lithium ions and a binder, and the electrode is in contact with the lithium salt.
  • the electric double layer capacitor As the electric double layer capacitor, a wound type electric double layer capacitor, a laminate type electric double layer capacitor, a coin type electric double layer capacitor and the like are generally known, and the electric double layer capacitor can also be in these types. .
  • a positive electrode and a negative electrode made of a laminate (electrode) of a current collector and an electrode layer are wound through a separator to produce a wound element, and the wound element is made of aluminum. And then filled with an electrolytic solution, preferably a non-aqueous electrolytic solution, and then sealed and sealed with a rubber sealing body.
  • separator conventionally known materials and structures can be used in the present invention.
  • a polyethylene porous membrane, polypropylene fiber, glass fiber, cellulose fiber non-woven fabric and the like can be mentioned.
  • a laminate type electric double layer capacitor in which a sheet-like positive electrode and a negative electrode are laminated via an electrolytic solution and a separator, and a positive electrode and a negative electrode are formed into a coin shape by fixing with a gasket and the electrolytic solution and the separator.
  • a configured coin type electric double layer capacitor can also be used.
  • reaction was quenched by adding 150.00 g of a saturated aqueous sodium chloride solution.
  • the reaction solution was extracted with diisopropyl ether and dried by adding magnesium sulfate. Subsequently, concentration and sublimation purification were performed to obtain 1.16 g of the objective 4-perfluorobutyl-vinylene carbonate (C 4 F 9 VC) as a white solid.
  • reaction was quenched by adding 100.00 g of a saturated aqueous sodium chloride solution.
  • the reaction solution was extracted with ethyl acetate and dried by adding magnesium sulfate. Subsequent concentration and sublimation purification yielded 4.73 g of the desired 4-perfluorohexyl-vinylene carbonate (C 6 F 13 VC) as a white solid.
  • Synthesis example 4 A 100 W high pressure mercury lamp was attached to a 1000 mL photoreactor, and 20.00 g of 4-perfluorohexyl-ethylene carbonate represented by the following formula and 197.00 mL of carbon tetrachloride were introduced.
  • reaction solution contains a carbonate represented by the following formula.
  • reaction solution obtained in the previous operation was introduced into a 1000 mL glass reaction vessel, and 5.98 g of triethylamine was added dropwise under ice cooling, followed by stirring for 3 hours. After the reaction ripening, 113.54 g of a 10% aqueous citric acid solution was added to quench the reaction, and magnesium sulfate was added to the organic layer obtained by the liquid separation operation and dried. Magnesium sulfate was filtered off and concentrated to obtain a crude 4-perfluorohexyl-carbonate.
  • the crude product was purified by sublimation to obtain 4.36 g of the desired 4-perfluorohexyl-vinylene carbonate (C 6 F 13 VC) as a white solid.
  • Synthesis example 5 A 100 W high pressure mercury lamp was attached to a 1000 mL photoreactor, and 20.00 g of 4-perfluorobutyl-ethylene carbonate represented by the following formula and 261.37 mL of carbon tetrachloride were introduced.
  • reaction solution contains a carbonate represented by the following formula.
  • reaction solution obtained in the previous operation was introduced into a 1000 mL glass reaction vessel, and 7.93 g of triethylamine was added dropwise under ice cooling, followed by stirring for 3 hours. After the reaction ripening, 150.64 g of 10% aqueous citric acid solution was added to quench the reaction, and magnesium sulfate was added to the organic layer obtained by the liquid separation operation and dried. Magnesium sulfate was filtered off and concentrated to obtain a crude 4-perfluorobutyl-vinylene carbonate.
  • the crude product was purified by sublimation to obtain 5.05 g of the desired 4-perfluorobutyl-vinylene carbonate as a white solid.
  • Synthesis Example 6 A reflux tube was attached to a 200 mL glass reaction vessel, 2.15 g of LiBr and 40.00 mL of N-methylpyrrolidone (NMP) were introduced, and the mixture was stirred at 35 ° C. for 1 hour. The inside of the reactor was replaced with carbon dioxide, and 10.00 g of an epoxy represented by the following formula was added dropwise, followed by stirring at 35 ° C. for 6 hours.
  • NMP N-methylpyrrolidone
  • reaction was quenched by adding 20 mL of a saturated aqueous sodium chloride solution.
  • the reaction solution was extracted with ethyl acetate and dried by adding magnesium sulfate. Subsequently, the carbonate shown by the following formula was obtained by concentrating.
  • the crude product was purified by distillation to obtain 3.77 g of the objective 4-trifluoromethyl-vinylene carbonate (CF 3 VC) as a colorless liquid.
  • CF 3 VC 4-trifluoromethyl-vinylene carbonate
  • Synthesis example 7 Into a 300 mL autoclave were introduced 10.00 g of vinylene carbonate, 103.65 g of perfluorohexyl iodide, and 1.02 g of t-butylperoxyisopropyl monocarbonate, and the mixture was stirred at 120 ° C. for 6 hours. After the reaction ripening, the reaction solution was concentrated to obtain a C 6 F 13 ECI crude product as a white solid.
  • C 6 F 13 ECI is a carbonate represented by the following formula.
  • Positive electrode in which LiNi 1/3 Mn 1/3 Co 1/3 O 2 , carbon black, and polyvinylidene fluoride (made by Kureha Chemical Co., Ltd., trade name KF-7200) are mixed at 92/3/5 (mass% ratio).
  • a positive electrode mixture slurry was prepared by dispersing the active material in N-methyl-2-pyrrolidone to form a slurry.
  • the obtained positive electrode mixture slurry is uniformly applied on an aluminum current collector, dried to form a positive electrode mixture layer (thickness 50 ⁇ m), and then compression molded by a roller press machine to form a positive electrode laminate. Manufactured.
  • a negative electrode current collector (thickness 10 ⁇ m) was prepared by adding styrene-butadiene rubber dispersed in distilled water to artificial graphite powder to a solid content of 6% by mass and mixing with a disperser to form a slurry. Were coated uniformly on the copper foil), dried to form a negative electrode mixture layer, and then compression molded by a roller press to produce a negative electrode laminate.
  • the positive electrode laminate and the negative electrode laminate were wound with a positive electrode and a negative electrode facing each other through a microporous polyethylene film (separator) having a thickness of 20 ⁇ m to prepare a wound body.
  • the wound body was put in an aluminum laminate, an electrolyte solution was injected, and the electrolyte solution sufficiently penetrated into a separator and the like, and then sealed, precharged, and aged to produce a 1 Ah lithium ion secondary battery.
  • the coin-type lithium secondary battery was examined for high voltage cycle characteristics and high temperature storage characteristics as follows.
  • Charging / discharging condition charge 1C, hold at 4.2V until charge current reaches 1 / 10C (CC / CV charge)
  • Example 2 A battery was fabricated and tested in the same manner as in Example 1 except that 4-perfluorohexyl-vinylene carbonate in Synthesis Example 4 was changed to 4-perfluorobutyl-vinylene carbonate in Synthesis Example 5. The results are shown in Table 1.
  • Example 3 A battery was fabricated and tested in the same manner as in Example 1 except that 4-perfluorohexyl-vinylene carbonate in Synthesis Example 4 was changed to 4-trifluoromethyl-vinylene carbonate in Synthesis Example 6. The results are shown in Table 1.
  • Comparative Example 1 A battery was fabricated and tested in the same manner as in Example 1 except that VC was further increased by 0.5 wt% (a total of 1.0 parts by weight of VC was added) instead of 4-perfluorohexyl-vinylene carbonate. The results are shown in Table 1.

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EP15861588.0A EP3205649B1 (en) 2014-11-21 2015-11-19 Fluorinated unsaturated cyclic carbonate and process for producing the same
US15/528,017 US10287263B2 (en) 2014-11-21 2015-11-19 Fluorinated unsaturated cyclic carbonate and process for producing same
PL15861588T PL3205649T3 (pl) 2014-11-21 2015-11-19 Fluorowany nienasycony cykliczny węglan oraz sposób jego wytwarzania
PL20152407T PL3667804T3 (pl) 2014-11-21 2015-11-19 Roztwór elektrolitu zawierający nienasycone cykliczne węglany, zawierające je urządzenie elektrochemiczne i litowo-jonowa bateria akumulatorowa
CN201580062686.XA CN107108550B (zh) 2014-11-21 2015-11-19 新型的氟代不饱和环状碳酸酯及其制造方法
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CN110062976B (zh) * 2016-12-26 2022-03-15 大金工业株式会社 电解液、电化学装置、锂离子二次电池、以及组件
CN110062976A (zh) * 2016-12-26 2019-07-26 大金工业株式会社 电解液、电化学装置、锂离子二次电池、以及组件
EP3522288A4 (en) * 2016-12-26 2020-08-26 Daikin Industries, Ltd. ELECTROLYTE SOLUTION, ELECTROCHEMICAL DEVICE, LITHIUM-ION SECONDARY BATTERY AND MODULE
US11043698B2 (en) 2016-12-26 2021-06-22 Daikin Industries, Ltd. Electrolytic solution, electrochemical device, lithium-ion secondary cell, and module
WO2018151019A1 (ja) * 2017-02-14 2018-08-23 セントラル硝子株式会社 立体選択的な二置換ハロゲン化エポキシドの製造方法
CN110546142A (zh) * 2017-04-27 2019-12-06 墨西哥氟石股份公司 方法
JP2020517717A (ja) * 2017-04-27 2020-06-18 メキシケム フロー エセ・ア・デ・セ・ヴェ 方法
US11377432B2 (en) 2017-04-27 2022-07-05 Mexichem Fluor S.A.De C.V. Method for preparing a tetrafluoro-1,2-epoxypropane
US11718597B2 (en) 2017-04-27 2023-08-08 Mexichem Fluor S.A.De C.V. Method for preparing a tetrafluoro-1,2-epoxypropane
CN110546142B (zh) * 2017-04-27 2023-09-05 墨西哥氟石股份公司 制备四氟-1,2-环氧丙烷的方法和包含四氟丙烯环氧化物的组合物
CN109134422A (zh) * 2018-06-08 2019-01-04 江苏长园华盛新能源材料有限公司 碳酸亚乙烯酯的制备方法
CN110327977A (zh) * 2019-06-21 2019-10-15 山西大学 一种铝锂双金属催化剂及其制备方法和应用
CN110327977B (zh) * 2019-06-21 2021-05-14 山西大学 一种铝锂双金属催化剂及其制备方法和应用

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EP3205649A1 (en) 2017-08-16
EP3667804A1 (en) 2020-06-17
JP6458808B2 (ja) 2019-01-30
CN110204525B (zh) 2022-01-28
PL3750884T3 (pl) 2022-07-11
CN107108550B (zh) 2020-03-03
EP3667804B1 (en) 2021-04-21
HUE054899T2 (hu) 2021-10-28
PL3205649T3 (pl) 2021-08-30
JP6989805B2 (ja) 2022-02-03
EP3750884A1 (en) 2020-12-16
CN107108550A (zh) 2017-08-29
HUE054520T2 (hu) 2021-09-28
EP3205649B1 (en) 2021-02-24
US20180346437A1 (en) 2018-12-06
US10287263B2 (en) 2019-05-14
JP2019024016A (ja) 2019-02-14
JPWO2016080484A1 (ja) 2017-08-03
PL3667804T3 (pl) 2021-11-02
US10464916B2 (en) 2019-11-05
CN110204525A (zh) 2019-09-06
EP3750884B1 (en) 2022-03-30
HUE059073T2 (hu) 2022-10-28
US20190185445A1 (en) 2019-06-20
EP3205649A4 (en) 2019-07-31
JP2020145199A (ja) 2020-09-10
JP6940468B2 (ja) 2021-09-29

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